The match was just 49 seconds old when Costa struck, leaving new Real Madrid coach Julen Lopetegui looking dumbstruck on the sidelines in Tallinn.
Costa was the target of a long ball from the back played by Diego Godin and beat Sergio Ramos in the air to nod the ball on.
The Spain striker reacted quicker than his international team-mate and latched on to his flick-on, then nodding the ball beyond Raphael Varane, striding into the right side of the box and rifling an emphatic strike past Keylor Navas from a seemingly impossible angle.
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