There were also scuffles between visiting fans and locals, with some wielding cafe tables as weapons, in a third day of violence in the narrow streets leading off Marseille's Vieux Port (Old Port).
Marseille's emergency services said about 10 people were injured during the fracas, including one middle-aged man who was knocked unconscious, and one England supporter had suffered a heart attack.
Water cannon trucks moved in and dozens of police armed with batons cordoned off streets, firing tear gas to break up the skirmishes.
"I hope they never reach the stadium," said Sabine Bernasconi, the mayor of one of Marseille districts
Broken glass and debris littered some roads and alleys near the Queen Victoria pub, focal point of clashes between English, Russian and French fans on Thursday and Friday.
The clouds of tear gas produced images of unrest all to similar, though on a much smaller scale, to those in the city 18 years ago when violence flared for two days and nights around England's World Cup game against Tunisia.
Local police chief Laurent Nunez said about 300 English fans had been involved and a similar number of Russians. There were no plans to close a beach-side fan zone, he said.
Police made six arrests on Saturday, adding to the nine from Friday. Those charged could face trial as early as Monday.
Pictures posted online showed Russian fans proudly displaying England flags captured during violent exchanges on Friday while groups of locals also weighed in, particularly with the throwing of bottles.
With up to 90,000 fans expected to fill the city, authorities were endeavoring to keep some sort of control and the atmosphere around the stadium and on the route to the fan zones was convivial.