Waving black and red anarchist flags, hundreds of students, made their way up the steps to parliament to the Tomb of the Unknown Soldier before riot police pushed them back.
Protestors also reportedly entered the main branch of the National Bank of Greece in the capital sending employees running in panic.
More school students were expected to mobilize in central Athens on Friday for further rallies and on Monday. Students occupied more than 400 school buildings across the country in protest.
The riots, which have spread to all corners of the country, are the worst in decades, destroying hundreds of shops, banks, buildings and cars in more than eight cities across Greece, including Athens and the port cities of Thessaloniki and Patras.
Gangs of hooded youths and self-styled anarchists have been smashing windows, looting shops and set up flaming barricades in streets across the country.
The violence was triggered by the police shooting of a 15-year-old boy last weekend but students have also been protesting growing corruption and economic and education reforms.
On Friday, dozens of students occupied the airwaves of radio station Flash for more than an hour, cutting programming to state their grievances against lying politicians, multinationals and journalists.
‘We are against the government and the growing power by the police who believe that they can shoot whenever and whomever they want,’ said Mario Bakiari, the president of the student body of the Athens district of Peristeri.
‘There is no way that the government can justify banks a 28- million-euro bail-out plan yet no money towards the educational system. Classes are without heating and many times are held in portables.’
The riots have spread beyond Greece’s border, hitting other European countries. Angry youths have reportedly also smashed shops, attacked banks and damaged police vehicles in Spain, France and Denmark.
Despite the intensity of the protests which have rocked the country for six consecutive days, public criticism over Prime Minister Costas Karamanlis and his ruling conservative government’s aloofness to the civil unrest increased.
The prime minister once again ruled out early elections during a press conference on the sidelines of an EU summit in Brussels on the economy on Friday.
‘The Bell Tolls for Karamanlis,’ the headline of the top-selling daily Ta Nea newspaper read.
The government, which has seen its popularity ratings fall sharply behind the opposition Socialists in recent months, promised once again to compensate businesses for the millions of euros of damage suffered – announcing loans, emergency subsidies and tax relief measures.
Store owners, which have suffered millions in damage, accused authorities of leaving their businesses unprotected as rioters smashed and burned their way through popular shopping districts. Although police have responded when attacked by firebombs, they held back when youths turned their rage against buildings and cars.
Many countries have issued travel warnings not to travel to Greece while the popular sites of Plaka and Monastiraki, located in the shadows of the Acropolis, were eerily empty of tourists. Even the Acropolis remained closed due to striking workers.
‘During one of the riots dozens of workers were trapped inside as hooded youths started to smash the windows,’ said Dimitra Anastasiadou of Zorpis Travel, which is located across the road from Athens University.
‘We called police for help but they told us there was nothing that they could do and told us to protect ourselves.’
The shooting of 15-year-old Alexandros Grigoropoulos by police on Saturday sparked days of rioting across the country.
A ballistics report into the shooting was due to be made public later Friday.
The State Secretary for Police, Panayiotis Hinofotis announced possible new measures for the Greek police force on Friday, which include determining which officers should be entitled to carry weapons and annual psychological tests.
All police in the Greek force have the right to carry loaded guns.