La Roja were stunned on penalties by the hosts at the Luzhniki Stadium, leaving the Selecao as market leaders ahead of their clash with Mexico
Brazil remain favourites to win the World Cup after Russia stunned Spain in the last 16
La Roja dominated for 120 minutes but were taken to penalties by the hosts, who won the shootout 5-3 after both Koke and Iago Aspas saw their spot-kicks saved.
Russia are now 22/1 (23.0) to go all the way and become the first team since France in 1998 to win the World Cup on home turf, with Brazil leading the way at 7/2 (4.50) and Les Bleus just behind at 15/4 (4.75).
It was a night to forget for the 2010 champions, who took the lead after just 12 minutes thanks to Sergei Ignashevich’s own goal but were pegged back before half-time when Artem Dzyuba levelled from the penalty spot.
The result leaves Belgium as 6/1 (7.0) third-favourites in the same market, and the Red Devils face 150/1 (151.0)Japan on Monday night wary of suffering a similar fate to Fernando Hierro’s men.
England, who are in action against a tricky Colombia outfit on Tuesday night, can also be found at 6/1 (7.0) to break their unwanted stretch of 52 years without a major trophy.