Portugal went ahead after just two minutes as Bernardo Silva capitalised on a defensive error to set up Renato Sanches, who opened the scoring with an unerring finish.
Dusan Tadic’s deflected strike levelled the scores later in the first half, with Rui Patricio partially culpable for allowing the ball to cross the line.
Substitute Mitrovic completed a dramatic turnaround in the 90th minute as he headed in from Tadic’s cross to send Serbia top of Group A and condemn Portugal to the playoffs.
Portugal enjoyed a dream start as Silva dispossessed Nemanja Gudelj before finding Sanches, who advanced into the area and rifled past Predrag Rajkovic.
Dusan Vlahovic thought he had equalised 10 minutes later as he struck towards the bottom-right corner, but his left-footed effort bounced off the post and away from danger.
Serbia did draw level in the 33rd minute when Tadic’s fierce strike from the edge of the area took a deflection, causing Patricio to fumble into his own net.
The hosts came within inches of reclaiming the lead after the interval as Sanches’ blocked effort was cleared against Rajkovic’s back and rolled just wide.
Serbia appeared surprisingly conservative in the second half but Mitrovic, who headed wide only minutes before, grabbed a dramatic winner as he nodded in at the back post from Tadic’s delivery to ensure his country’s place in Qatar.
What does it mean? Serbia on the plane to Qatar, Portugal in the play-offs
Portugal simply needed to avoid defeat to remain top of Group A, heading into the game level on points with Serbia but ahead on goal difference, with their head-to-head records irrelevant as the pair drew the reverse fixture 2-2.
The 2-1 defeat sees Fernando Santos’ men slip into the playoffs, however, with Serbia leapfrogging them into an automatic qualifying spot at the final hurdle.
Terrific Tadic
While Mitrovic will hit the headlines for his late winner, Tadic was directly involved in both goals – scoring the equaliser before setting the Fulham striker up late on.
The Ajax forward found the target with both of his two shots and created two chances – including the assist – as he spurred his side on to victory.
No Ronaldo to the rescue
Cristiano Ronaldo failed to score for the second successive Portugal game after being shackled in the 0-0 draw with the Republic of Ireland last time out.
The all-time leading scorer in men’s international football managed three shots against Serbia but failed to hit the target with any of them in an unusually quiet showing.
What’s next?
Portugal must now wait to find out who they will be drawn against in the playoffs, while Serbia’s automatic qualification place sees them avoid the extra fixtures.
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