Sergio Ramos equalled Iker Casillas's record of 167 appearances for Spain on an emotional night at Sporting Gijon's El Molinon stadium, which paid tribute to the late Spain and Sporting forward Quini before kickoff.
He made it 3-0 with a superb first-time finish into the bottom corner in the 20th minute, scoring his first ever treble in a competitive game, more than 19 years after making his professional debut.
World Cup hosts Russia got their Nations League campaign off to a flying start with a 2-1 win away to Turkey thanks to goals from Dennis Cheryshev and Artem Dzyuba on Friday.
Real Madrid dropped points for the third time in seven games since Zinedine Zidane's return as they were held to a 0-0 draw away to Getafe in La Liga on Thursday, which harmed their neighbours' hopes of a top-four finish.
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Gonzalo Higuain pulled one back three minutes later with a typically opportunist goal, the Argentine's 13th in the league this season, to set up a tense final half hour.
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Goals from Henrikh Mkhitaryan, who made a mockery of his two-month exile from the starting lineup with a superb individual effort, and Zlatan Ibrahimovic secured an easy win that banished memories of their earlier group stage struggles.
It will have made uneasy viewing for coach Jorge Sampaoli and emphasised more than ever how reliant his side are on their talisman Messi, who has been struggling with a muscle problem.
News of all that's transpired on and off the football field
News of all that's transpired on and off the football field
Paulo Dybala came off the bench to give unbeaten Serie A leaders Juventus a 1-0 win away to a brave Bologna side who had the better of the match and hit the post in stoppage time on Sunday.
News of all that's transpired on and off the football field
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