The clashes sprang from a massive demonstration that drew an estimated 40,000 workers to the streets in the first major labor protest this year.
Riot police fired tear gas at young protesters, who hurled stones, petrol bombs and firecrackers at government buildings. Thick smoke blanketed much of the city for hours, sending demonstrators and bystanders scrambling for cover.
One policeman was injured when youths threw a Molotov cocktail at him, setting his jacket and uniform ablaze. He was rescued by colleagues.
Throughout the center of Athens, rioting youths smashed concrete slabs, banks and marble balustrades outside the capital's main metro station.
Protests against the government's austerity measures also swept other major cities, while the general strike paralyzed the country, keeping more than 100 flights grounded, ships docked and trains idle. Public schools and agencies were shut while state-run hospitals operated with emergency staff.
The unrest rekindled fears violence would spread if Greece fails to revise the terms for the repayment of its debt, which is among the highest in the 27-nation European Union.
On a visit to Finland, Prime Minister George Papandreou tried to sympathize with the peaceful protesters.
"The economic situation [in Greece] is very difficult, and sometimes even I myself feel an urge to join the ranks of protesters," Papandreou was quoted as saying to Finnish national broadcaster YLE. "Still, mere protesting leads nowhere. We need decisions that can genuinely help fix the problems."
Papandreou signed off on a rash of radical cost-cutting measures in May in exchange for a $146 billion bailout patched together by Greece's European partners and the International Monetary Fund.
The IMF has been pressing Greece to speed up reforms to avoid missing its economic goals.
Leading U.S. and European economists have been prodding Greece to restructure its debt -- an option that Athens has repeatedly rebuffed, saying it would prove "catastrophic."
Union leaders fear shortfalls in state revenues may spell additional pension and salary cuts for the crisis-weary Greeks.
Trade unions staged eight general strikes last year. Most were marred by violent clashes, including an arson attack on a bank that killed three employees.

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