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KYIV, Ukraine — A long column of Russian trucks laden with relief supplies rumbled toward war-torn eastern Ukraine on Tuesday, unsettling Ukrainian officials who warned that any attempt by Moscow to deliver humanitarian aid without their consent would be treated as an invasion.

The convoy’s departure — announced on Russian television as an Orthodox priest sprinkled holy water on the tractor-trailers — raised fears among Western officials that Russia’s planned aid for the devastated region was a ruse to boost the combat capability of pro-Russian rebels there.

By day’s end, Russia and Ukraine appeared to have worked out a rough agreement that Russia would deliver the contents of the 198 trucks to the International Committee of the Red Cross at a Ukrainian-controlled border post near the city of Kharkiv. But important questions remained about the logistics of delivering the aid to hard-hit areas of eastern Ukraine, including whether the Russian vehicles would be allowed to cross the border.

Ukrainian officials appeared to have little faith in their Russian counterparts, accusing them of funneling weaponry to rebels and then saying Russia’s aid was needed to stanch the ensuing humanitarian catastrophe. Russia has denied helping the rebels.

“Russia is playing an absolutely cynical game,” Ukrainian Deputy Foreign Minister Danylo Lubkivsky said Tuesday. In eastern Ukraine, “they are trying to use the pretext of humanitarian aid and assistance, and it seems they are just running out of excuses for their aggression.”

Ukrainian, U.S. and NATO officials have been cautious about the Russian aid offers, fearing that they could simply be a pretext to boost the rebels.

Ukrainian officials said Tuesday that there were ongoing negotiations about the structure of any humanitarian assistance to Ukraine from international partners, including Russia, but that plans would not be in place for up to a week. Important questions remained unanswered, they said, including the scope of civilian needs in eastern Ukraine and the willingness of rebels in the Luhansk region to facilitate aid distribution.

“Ukraine is ready to receive from our partners. If Russia gets involved, we don’t mind, but it should happen according to our rules,” said the deputy head of Ukraine’s presidential administration, Valeriy Chaly.

But he said that any assistance that reaches Ukraine’s borders would need to be examined and handed over to the Red Cross for delivery. He warned that attempts to bring anything across the border without the consent of the Ukrainian government would be treated as an act of aggression.

“If we have some surprise,” he said, “we will react as an independent sovereign country must react.”

The Russian Foreign Ministry said Tuesday evening that it would follow Ukrainian requests about routes for transportation and inspection and that it would bring the convoy — totaling 262 vehicles, including the cargo-laden trucks — to the border near the Ukrainian-held city of Kharkiv. But it said there were “puzzling statements” from Kyiv about “new logistics requirements,” an apparent reference to the demand that the convoy not be allowed into Ukraine.

At a news briefing in Kyiv, Ukrainian military spokesman Andriy Lysenko played a covertly recorded video that he said showed the Russian aid was connected to the Russian military. Trucks similar to the ones that Russian state television showed leaving for Ukraine were lined up on what Lysenko said was a military base. Soldiers wearing uniforms could briefly be seen lined up in front of some of the trucks. One implication was that Russian military personnel were driving the trucks.

Western leaders said aid to Ukraine needs to be coordinated with the Ukrainian government.

Secretary of State John F. Kerry said during a visit to Australia that diplomatic efforts are underway to resolve tensions over the Russian shipments. He said diplomats from Germany, Ukraine, Russia and other countries are trying to find an acceptable means “to deliver humanitarian assistance without the guise of a military delivery . . . against the will and wishes of a country where it is being delivered and against the norms of the . . . International Red Cross.”

Kerry spoke following two days of talks in Australia, which lost 38 citizens aboard a Malaysia Airlines flight that was shot down over rebel-held territory in eastern Ukraine last month. The Boeing 777 was carrying 298 passengers and crew on a flight from Amsterdam to Kuala Lumpur.

French President Francois Hollande spoke by telephone to Russian President Vladimir Putin on Tuesday and “expressed worries over the developments in eastern Ukraine” and about “the prospect of a unilateral Russian mission to Ukraine,” Hollande’s office said in a statement.

Russian state television showed white-painted Kamaz trucks without license plates packing up at dawn near Moscow and departing for the Ukrainian border. At least one appeared to be flying a Red Cross flag; others flew the flag of Russia. The Russian Foreign Ministry said the trucks were carrying grain, salt, sugar, baby food, water, medicine and medical equipment, as well as 12,000 sleeping bags and 69 portable power generators. The total weight of the goods was nearly 2,000 tons, the ministry said.

Ukraine’s lead negotiator in the talks about humanitarian aid, former president Leonid Kuchma, said Tuesday that the aid must be kept away from the rebels.

“The way this aid will be distributed is highly important,” Kuchma told the Interfax news agency. “First and foremost, it should be provided to hospitals, kindergartens, orphanages and other people who need it. The militants must not receive even a gram.”

State television quoted truck drivers as saying that the convoy would take two to three days to reach the Ukrainian border. The distance from Naro-Fominsk, the town where the convoy departed, to Kharkiv is about 425 miles.

The Red Cross office in Kyiv, which would coordinate the distribution of any aid, was not informed by Russian authorities prior to the convoy’s departure, a spokesman for the office said.

“There are talks now with the Ukrainian authorities to try to sort out the situation,” said the spokesman, Andre Loersch.

Ukrainian officials have said they fear that any Russian aid convoy could be used as a pretext for a fuller military intervention from Russia, which has massed tens of thousands of troops at the border with Ukraine, according to Western officials.

Intense fighting in eastern Ukraine in recent weeks has put significant pressure on rebels, who now say they are encircled in their stronghold of Donetsk. Rebels also control Luhansk, to the east, where city officials said Monday that residents had been without power or water for nine days.

The convoy departed a day after NATO Secretary General Anders Fogh Rasmussen warned that there was a “high probability” of a Russian military intervention in Ukraine.

“We see the Russians developing the narrative and the pretext for such an operation under the guise of a humanitarian operation, and we see a military buildup that could be used to conduct such illegal military operations in Ukraine,” Rasmussen told the Reuters news agency.

Anne Gearan in Sydney contributed to this report.