The eight-metre bronze statue depicted a Ukrainian and Russian worker on a plinth, holding aloft together a Soviet order of friendship.
The statue was underneath a giant titanium People's Friendship Arch' erected in 1982 to commemorate the 60th anniversary of the Soviet Union.
"We now see what this "friendship" is - destruction of Ukrainian cities ... killing tens of thousands of peaceful people. I am convinced such a monument has an entirely different meaning now," Kyiv mayor Vitaly Klitschko said on Tuesday.
Workmen started by removing one of the two bronze heads, which fell to the ground with a hollow clang.
As a crane lifted the monument off its moorings and gradually lowered it to the ground, a crowd of about 100 people cheered and shouted "Glory to Ukraine" and other slogans.
Russia's invasion of Ukraine, launched on February 24, has left thousands dead or injured, reduced towns and cities to rubble, and forced more than 5 million people to flee abroad.
Moscow calls its actions a "special operation" to disarm Ukraine and protect it from fascists.
"We should not have any relations with the nation of aggressors ... no friendship, no relations, nothing," said Diana, a young woman, who did not give her full name.
Klitschko said the arch would remain in place but be renamed the Arch of Freedom of the Ukrainian People.