Ukrainian troops have entered the eastern town of Kramatorsk a day after an operation began to recapture areas seized by anti-government separatists.
But they were blocked by civilians and the situation is unclear, amid reports that some may have abandoned their vehicles or even changed sides.
In the city of Donetsk, which has seen weeks of unrest, pro-Russian gunmen seized control of the mayor's office.
Meanwhile Nato announced it was beefing up its eastern members' defences.
As tensions rose, Ukraine's acting Defence Minister, Mykhailo Koval, was said to be travelling to the east of the country to monitor the progress of the "anti-terrorist operation" announced by acting President Olexander Turchynov the previous day.
The interim Prime Minister, Arseniy Yatsenyuk, called on Russia to "stop supporting terrorists in Ukraine".
The crisis escalated in eastern parts of Ukraine this month after pro-Russian rebels seized buildings in about 10 towns and cities, demanding greater autonomy or referendums on secession.
Tens of thousands of Russian soldiers are believed to have massed on Ukraine's borders since Russia took control of the Ukrainian region of Crimea last month, following a controversial referendum on self-determination.
'Not to fight'
After Ukrainian forces recaptured an airfield outside Kramatorsk on Tuesday, armoured vehicles appeared in the centre of the town early on Wednesday.
BBC journalists witnessed civilians, at least some of whom appeared to be local people, challenging soldiers, who were also blocked by a crowd a few kilometres outside the town.
One officer said he had not "come to fight" and would never obey orders to shoot his "own people".
Villagers have confronted Ukrainian soldiers in the villages of Novoselivka and Ivanivka near Kramatorsk
Video later emerged of six armoured personnel carriers, flying Russian flags, entering the nearby town of Sloviansk.
According to Reuters news agency, they included some of the same Ukrainian troop carriers which were stopped in Kramatorsk.
A soldier guarding one of the carriers told the agency he was a member of Ukraine's 25th airborne brigade from Dnipropetrovsk, a city also in eastern Ukraine.
He said the soldiers had had no food for four days until local people fed them.
"All the soldiers and the officers are here," he said. "We are all boys who won't shoot our own people."
The Ukrainian army told AFP news agency it had no reports of any of its equipment being seized.
In Donetsk, where activists have been occupying the regional government building since 6 April, gunmen met no resistance as they entered the mayor's office.
They told an AFP correspondent their only demand was for the region to stage a referendum on turning Ukraine into a federation with broader local rights.
Russia accused
In Brussels, Nato Secretary General Anders Fogh Rasmussen promised "more planes in the air, mores ships on the water, more readiness on the land".
He called on Russia to make clear it did not "support the violent actions of well-armed militias or pro-Russian separatists in eastern Ukraine".
The Nato alliance includes two ex-Soviet Baltic republics with large ethnic Russian communities, Latvia and Estonia, while other members such as Poland share borders with Russia.
Four-way talks are due to take place on Thursday in Geneva between diplomats from Russia, the EU, the US and Ukraine.
Ukrainian and Western officials have accused Russia of being behind the pro-Russia activism in the region while Moscow denies fomenting the unrest.
Ahead of the annexation of Crimea, masked soldiers believed to be Russian troops appeared at strategic points across the peninsula alongside "self-defence" units, said to have been formed locally.
Speaking in London, UK Foreign Secretary William Hague said Russia had sent "thinly disguised" armed groups into eastern Ukraine to spearhead the occupation of buildings.
The US has said it is "seriously considering" adding to sanctions imposed after the annexation of Crimea. It described Ukraine's military operation as a "measured" response to a lawless insurgency.
At the scene
People are very nervous. Many have not slept for several nights. When Ukrainian armoured personnel carriers appeared in the town, people quickly surrounded them. Some accused soldiers of "acting against their own people."
"Why did you come to our land?" a man from the crowd asked. "Why are you driving over our fields? We are peaceful people! And we just want our demands to be respected!"
Soldiers were sitting on the APCs with automatic guns, in full combat gear. "I know they can shoot at us, but we are miners, we see death every day," the man said. "So we are not afraid. We will stand here until victory. We want a referendum to be held. We should decide our future for ourselves."
"We are just obeying orders, let us go!" the commander shouted. "We didn't come here to fight. We are just moving around. I will never shoot at my own people!"
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