"It was a genocide, an attempt to subjugate the nation, deliberately planned and put into effect," charged pro-Western President Viktor Yuschenko in a speech to thousands gathered in the centre of the capital.
"Its organiser and executor was the communist totalitarian regime," he said, adding that "the crimes of bolshevism and communism are identical to those of Nazism."
Some four to 10 million people are estimated to have starved to death as a result of a Soviet programme of forced collectivisation launched by dictator Josef Stalin in 1932.
Ukrainian farmers had their produce confiscated and the Soviet authorities also blocked food supplies into Ukraine in what some historians have argued was a deliberate attempt by Stalin to crush a drive for independence.
For years Kiev has been trying to get the United Nations to recognise the famine as "an act of genocide" committed against the Ukrainian people, though pro-Russian Ukrainians say it resulted from ideological error.
A law officially calling the famine genocide was passed only last year by the Ukrainian parliament, and by a slim majority.
Saturday's commemorations began in the 11th century St Sophia's cathedral in central Kiev in a service televised live and attended by Yushchenko and his family. They were flanked by interim Prime Minister Viktor Yanukovich, a pro-Russian, and ministers representing the gamut of the country's political parties.
"We pray for the peace of God's servants killed by the famine in Ukraine," a priest wearing a gold chasuble chanted, and a choir responded, "Eternal memory."
The president then led several thousand people bearing flags adorned with black ribbons to a monument to the victims of the famine, followed by a minute of silence across the country.
The gathering, including Yushchenko, then began lighting thousands of candles on central Saint Michael's Square.
In his speech the president called the famine the "greatest catastrophe" to have struck Ukraine, and urged "world condemnation of communist terror" that had killed innocent people, including Russians, Belarussians and Tatars as well as Ukrainians.
Ukraine finally gained its independence with the collapse of the Soviet Union in 1991.