The Ukrainian flag was raised by the city on Thursday as a ‘gesture of solidarity to its people’.
Russian forces have launched a major military assault on country with missile strikes and explosions recorded near major cities.
In a statement, mayor Joanne Anderson described the invasion as a “very dark day which could easily become a defining one of the 21st century”.
She said: “I hope and pray all Western nations remain calm, clear and resolute in their support of Ukraine and its people.
“For all the Ukrainians who have made Liverpool their home, this is a deeply troubling time, we will do what we can to support you.”
There are around 3,000 Ukraine-born residents living in the North West of England, according to official figures from the Office of National Statistics.
The data, for the period July 2020 to June 2021, also reveals there are approximately 6,000 Russian-born residents living in the region.
Mayor Anderson added: “There are no winners in war. We must now strain every sinew to convince president Putin of that fact.”
The Cunard Building and St George’s Hall will be lit up in the Ukrainian colours, blue and yellow, at dusk.