CCTV footage shows a rocket hitting the apartment block as officials urge locals to take immediate shelter.
Russian troops reached the Ukrainian capital and attacked a military base in the city, as well as attempting to capture an electricity generation station.
Reuters has reported that Kiev has been struck by two missiles in the southwest areas of the city center.
More than 120,000 Ukrainian refugees have so far left the country since Russia began its attack on its neighboring country this week, the United Nations refugee agency said Saturday.
The situation was expected to get worse, the UN Deputy High Commissioner for Refugees, Kelly Clements, said.
“We now see over 120,000 people that have gone to all of the neighboring countries,” she said. “The reception that they are receiving from local communities, from local authorities, is tremendous. But it’s a dynamic situation. We are really quite devastated, obviously, with what’s to come.”
Most are heading to Poland and Moldova, but also to Romania, Slovakia and Hungary, the UN said.