Ukraine's defence ministry is telling Kyiv residents to make Molotov cocktails to help defend the capital against invading Russian forces on the second day of their fast-moving offensive.
Russian President Vladimir Putin, meanwhile, called on the Ukrainian army to fight the country's leadership.
Yet even as the fighting intensified and swathes of Ukraine came under siege, Russia proposed sending a delegation to the Belarusian capital Minsk to hold peace talks with Ukrainian officials.
The Kremlin said that after it made the proposal, the Ukrainians countered with the suggestion that talks be held in Warsaw instead but then contact was paused, Russian news agencies reported.
Officials in Kyiv have yet to publicly comment.
Ukrainian President Volodymyr Zelenskiy had twice made the offer to conduct talks with Putin if it would prevent violence.
Zelenskiy has floated the idea that his government could adopt a non-aligned or neutral status.
Other officials in Kyiv have been more specific, saying Ukraine could promise to stop working toward NATO membership.
The focus on Friday was squarely on Kyiv, a city of three million people, whose streets and squares had emptied out amid the sound of air raid sirens and fears it could fall to Russian forces within days.
Thousands of people were taking shelter in metro stations after overnight Russian strikes that Ukraine's foreign minister called "horrific" and on a scale not seen since World War II.
There were reports of fires breaking out at a multi-storey residential building on the eastern bank of the Dnipro river after it was hit by a missile.
Russian troops reached the northern outskirts of the city by Friday morning.
In response, the defence ministry told people to "come to the streets with Ukrainian flags (and) film the Russian occupiers".
The ministry called on locals to prepare petrol bombs for use in combat and to report sightings of Russian military equipment.
"The city is in defence mode," Kyiv Mayor Vitali Klitchko said, according to the UNIAN news agency.
Gunfire and explosions in some areas meant Russian "saboteurs" were being taken out.
Russian authorities said the strategically important Hostomel airfield, northwest of Kyiv, had been captured.
They said 200 Ukrainians had been "neutralised" in the process.
In video captured by CNN, former Ukrainian president Petro Poroshenko was seen on a Kyiv street holding a gun and surrounded by defence forces.
He told the network he would help defend the country and called Putin "simply crazy".
Ukraine's armed forces said 2800 Russian military personnel have been "lost" since the invasion started.
It did not say if they were killed, wounded or captured.
The Russian defence ministry, on the other hand, has said there have been no significant casualties.
Zelenskiy said early on Friday that 137 Ukrainian soldiers were killed.
The toll on soldiers and civilians was impossible to confirm.
Beyond Kyiv, there were renewed air strikes and fighting along various battle lines across Ukraine.
Thirty-five civilians have been injured in attacks on Mariupol in southern Ukraine, the city's mayor said, accusing fighters supporting pro-Russian separatists of shooting at civilian buildings.
Zelenskiy has also accused Russian forces of targeting the civilian population although Russia says it is only going after military targets.
Officials in Kyiv and Washington DC have said that Russia's ultimate objective is to overthrow the Ukrainian government.
Earlier, Zelenskiy denied reports that he had left Kyiv, vowing to stay in the capital with his fellow citizens come what may.
The United States, United Kingdom and the European Union are among those who have responded to the invasion with far-reaching sanctions against Russia, including on its financial sector.
In the most direct hit on the Russian leadership yet, diplomatic sources told the DPA news agency EU foreign ministers adopted new sanctions targeting Putin and his Foreign Minister Sergei Lavorv for invading Ukraine.
Putin and his foreign minister are subject to an asset freeze as part of a massive package agreed on at an emergency EU leaders summit on Friday.
Meanwhile the 47-country Council of Europe has suspended Russia due to its attack on Ukraine, the Committee of Ministers decided on Friday.
Also on Friday, Russia banned British aircraft from using its airspace, in a tit-for-tat response a day after Russia's Aeroflot airline was barred from flying to the UK.
Poland and the Czech Republic followed up later by saying they would also close airspace to Russian planes.
NATO members also said they had agreed to send rapid response troops to protect allies near Russia and Ukraine.
Putin says he does not plan a military occupation, only to disarm Ukraine and remove its leaders.
But it is not clear how a pro-Russian leader could be installed unless troops control much of the country.
Russian state media have relentlessly characterised Ukraine as a threat but thousands of Russians protested against the war.
Hundreds were swiftly arrested.
Ukrainians were circulating an unverified recording on Friday of a Russian warship ordering a Ukrainian Black Sea outpost to surrender.
The Ukrainians reply: "Russian warship, go f*** yourself."
Zelenskiy said the 13 guards were killed by a Russian strike and would receive posthumous honours.
Ukrainians were fleeing into neighbouring Poland, Romania, Hungary and Slovakia, mostly women and children after authorities in Kyiv restricted passage for men between 18 and 60 years old.
with reporting from Reuters