England won the game 1-0, but the day was marred by widespread violence in this Belgian town.
English fans threw bottles at police as they left the stadium and smashed windows at a McDonald's in the town. During the game, ticketless England supporters stormed through bars and cafes, venting their frustration at failing to get into the stadium.
Earlier in the day, fans attacked each other with plastic furniture from the town's cafes. Another 28 were detained for drinking and rowdiness in Brussels, the Belgian capital 30 miles from Charleroi.
Several people were injured in the day of sporadic violence, Charleroi Mayor Jacques van Gompel said, but none seriously.
The latest detentions brought this week's total to 850.
On Friday night, British fans rioted near the central square of Brussels. Police used tear gas and water cannons and detained 374 English people. By Saturday, they began shipping them back home aboard Belgian military aircraft.
Fears of violence had dogged the tournament for months, but the first week was nearly incident-free.
By Saturday morning, though, Charleroi's main square was crowded with 2,000 drinking fans. Officers moved in to effectively partition the square into German and English zones.
German fans shouted "Deutschland! Deutschland!" English fans responded with "Rule Britannia" as riot police tried to keep them apart.
Jet hoses from tank-like vehicles doused the fans, who hurled tables, chairs and garbage across the square. The water cannons swept some fans off their feet and washed them into side streets, where they were followed by officers on horseback.
Police spokeswoman Els Cleemput said one Englishman was arrested after attacking a policeman, and 20 were found carrying weapons, mainly knives.
English fans flown to Manchester, England, complained the Belgian police had used excessive force and made indiscriminate arrests.
But Home Affairs spokesman Simon Hughes said in London that "the Belgian authorities have our full support in being as tough as necessary on the English visitors who are behaving not like fans but like hooligans.
"England football fans are sick to the back teeth of our fellow-countrymen who behave like animals," he said.
By IAN PHILLIPS