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Kolarov, captain of his country for the tournament in Russia, scored the only goal of the game against Costa Rica to set his side off to a winning start.
The left-back delivered a trademark free-kick that beat goalkeeper Keylor Navas all ends up, a decisive moment in the contest.
It was a stunning moment from Kolarov, who enjoyed an impressive first season with the Giallorossi last term.
He was subsequently named Man of the Match for his heroics.
It was also the first victory for a Roma player at this summer's tournament. On Saturday, Federico Fazio was an unused substitute as Argentina were held to a 1-1 draw against Iceland.
Later on Sunday night, Alisson Becker suffered similar frustration as Brazil were pegged back in a 1-1 draw against Switzerland.
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