The confrontation, described as the worst in the city for 30 years, began when protesters attempted to push through a police cordon in Syntagma Square in the centre of the city. A small group separated from the main crowd and began throwing petrol bombs and red paint at police, who responded with volleys of CS gas.
Broken glass from the Molotov cocktails mingled with the smashed windows of shops as clouds of gas hung in the air, driving marchers out of the square towards the United States embassy.
Thousands waved red banners, rainbow flags, and placards denouncing Tony Blair for his role in the Iraq conflict.
A faction of the Greek Communist Party occupied the headquarters of British Airways, unfurling a banner that denounced "Killers, Imperialists". Protesters threw rocks, bottles of paint and petrol bombs at the Italian and British embassies. Shop fronts, bus stops and rubbish bins were smashed and set on fire.
The violence embarrasses Greece's socialist government, which is midway through an EU presidency already troubled by Europe's sharp divisions over the Iraq war. Anti-American sentiment runs high in a country where opinion polls have consistently shown more than 95 per cent of Greeks oppose the conflict in Iraq.
Daily marches have been held since the conflict began and protest groups are angry at the government for opening Greek airspace to the US military and placing no restrictions on the use of an American navy base in Crete.
"Europe was wounded by the support some countries, especially Britain, gave to the United States over the war," the newspaper Eleftherotypia said yesterday. "These defectors must return [to the EU] after their criminal blunder."
Police estimated more than 8,000 protesters were involved in the clashes. At least five people were injured, including a police officer and a cameraman, and the police said they had arrested more than 50 demonstrators.
The Greek authorities, who were expecting the protests, had mounted an unprecedented security operation in the city. Some 20,000 police officers were on duty, and many streets were blocked off.
The Acropolis and several other ancient sites and museums were closed to the public, while road access to Athens airport was disrupted by the security.
The government declared a public holiday in the city, as traffic restrictions across the capital made commuting impossible.
The Agora, the heart of ancient Athens, provides the backdrop to the summit. The centrepiece ceremony, which saw the signing of the EU's accession treaty yesterday, took place at the Agora's Stoa of Attalos, a massive colonnaded monument at the foot of the Acropolis that was restored in the 1950s. It is only the second time the Stoa of Attalos has been used for a public function. It was used in 1985 for hosting an exhibition when Athens was the Cultural Capital of Europe.
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