Supporters were seen running through the streets before officers attempted to disperse them by firing the gas into the crowds.
Fans from England, Wales, Slovakia and Russia have been gathering in the city for Group B matches between the countries.
A large group of fans were congregated at the Place des Reignaux when officers used the spray and let off a canister. A loud bang was also heard.
Supporters held their shirts over their mouths and left the scene rubbing their eyes and spitting.
Hoards of fans were seen walking through the streets chanting “England, England, England.”
In footage posted online by ex-England footballer Stan Collymore, one man wearing a green hat is seen smashing wing mirrors off cars parked on the street.
Collymore said: “Somebody threw a, not a grenade, something that went bang towards some England fans and the England fans have just run.”
The bang caused the crowd to surge forward and they dispersed as police fired tear gas.
Around 10 men wearing Russian Ultra t-shirts were seen walking away from the area.
Flares were also let off during Russia’s defeat by Slovakia in Lille. Slovakia won 2-1.
Uefa handed out a suspended disqualifaction to Russia yesterday and warned the Russian Football Union that if there was any more violence inside the stadium involving their fans the suspension would be lifted and Russia would be expelled from the tournament.