STORY: Lviv mayor Andriy Sadoviy said at least seven people were killed and 11 were wounded. The blast shattered windows of a hotel housing Ukrainians evacuated from elsewhere in the country, he added.
Emergency teams rushed to the site to extinguish the fire at the facility.
Separately, authorities said some of the missiles hit areas close to a railway station and other railroad facilities, briefly disrupting normal traffic.
Russia denies targeting civilians and rejects what Ukraine says is evidence of atrocities, saying Ukraine has staged them to undermine peace talks.
Russia invaded Ukraine on Feb. 24 and calls its action a special military operation to demilitarise Ukraine and eradicate what it calls dangerous nationalists.
The West and Kyiv accuse Russian President Vladimir Putin of unprovoked aggression.