Nadezhda Tolokonnikova dismissed the amnesty law that set her free, saying it was a “cosmetic measure”.
She and band-mate Maria Alyokhina, who was also freed, said the prison system needed wider reform and promised to continue anti-government action.
Nadezhda Tolokonnikova and Maria Ayokhina were jailed in 2012 after singing a protest song in a Moscow cathedral.
The act was seen as blasphemous by many Russians, and was condemned by the Orthodox Church.
But their conviction for “hooliganism motivated by religious hatred” was criticized by rights groups, anti-government activists and foreign politicians.
The amnesty passed last week aimed to free some 20,000 prisoners.
Both Pussy Riot members said their anti-government stance had not softened, and both promised to form a human-rights group to fight for prison reform.
Nadezhda Tolokonnikova, who was freed from a prison hospital in the Siberian city of Krasnoyarsk, immediately called for a boycott of the Sochi Games.
“What is happening today – releasing people just a few months before their term expires – is a cosmetic measure,” she said.
“That includes the case of Khodorkovsky, who didn’t have much time left on his prison term. This is ridiculous.”
She said far more people should be set free.
“I’m calling for a boycott, for honesty. I’m calling [on Western governments] not to give in because of oil and gas deliveries from Russia.”
Nadezhda Tolokonnikova, 24, labeled the Russian state a “totalitarian machine” and said prison reform was the starting point for reform of Russian society.
Maria Alyokhina, released in the city of Nizhny Novgorod, 280 miles east of Moscow, told Russian TV that the amnesty was “a profanation”.
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