The defender had been on the pitch for just a matter of minutes after replacing Marcelo, but hit home with an excellent strike from out wide to decide matters
Substitute Nacho grabbed the only goal as Real Madrid qualified for the Champions League last-16 with a hard-fought victory over Paris Saint-Germain on Tuesday. The 10-time European champions initially struggled to get going at the Santiago Bernabeu and the French visitors looked the stronger side throughout the first half of the Group A clash.
However, an opportune finish from defender Nacho, helped by some awful positioning from PSG shot-stopper Kevin Trapp, proved decisive.
PSG responded excellently by bombarding the hosts' goal, Adrien Rabiot and former Madrid winger Angel Di Maria both hitting the woodwork, but the home side held on.
Malmo's 4-0 defeat at Shakhtar Donetsk meant Madrid are guaranteed a top-two finish with two more games to go while PSG's undefeated run in 2015-16 is at an end.
Madrid boss Rafa Benitez recalled captain Sergio Ramos and first-choice goalkeeper Keylor Navas to the hosts' line-up after the pair missed Saturday's 3-1 triumph over Las Palmas, while Laurent Blanc strengthened his XI with Zlatan Ibrahimovic, Marco Verratti, Thiago Motta and David Luiz all coming in.
The match began with the same defensive robustness that was displayed two weeks ago when they played out a 0-0 stalemate at Parc des Princes.
The flow of the game was punctuated by a series of injuries 10 minutes in. Serge Aurier and Isco collided heads, with the latter requiring treatment on the sidelines to stem the bleeding, before Verratti was forced off shortly afterwards with a calf injury.
PSG were the better side in the early stages and, after 22 minutes, Ibrahimovic collected the ball on the edge of the box and curled a shot inches wide of the bottom-right corner.
The veteran Sweden striker, who became PSG's all-time top goalscorer earlier this season, triggered further gasps around the Bernabeu shortly afterwards when his dipping free-kick only just skidded the wrong side of the same post
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But for all PSG's pressing, it was Madrid who took the lead with 35 minutes played. Toni Kroos' hopeful shot deflected off Thiago Silva's outstretched leg and into the path of Nacho, who had just been brought on for the injured Marcelo.
PSG goalkeeper Trapp made the mistake of watching the looping ball rather than the man and the makeshift left-back deftly placed it into the back of the net off the post from an acute angle.
Rabiot, Verratti’s replacement, almost equalised immediately by slamming an effort against the post from the edge of the box, then Maxwell's enticing cross somehow evaded Edinson Cavani and Ibrahimovic a few minutes later.
Former Napoli man Cavani will have been furious with himself in first-half stoppage-time when, one-on-one with Navas, he fluffed his attempted chip and watched as his tame shot was cleared off the line.
The Ligue 1 table-toppers continued their momentum in the second half as a launched through ball put Di Maria through on goal but, despite a fine first touch, the Argentine shot straight at Navas.
It wasn't all PSG, however, and Trapp was forced into a reaction save when Isco's 30-yard strike cannoned off David Luiz's back and towards the top corner before the German tipped it off target.
Madrid dampened PSG's attacking intent as the second half wore on and Isco's lashed effort from close range required Trapp to save with his legs to keep the hosts only one goal up.
Di Maria almost had the final say late on but his effort struck the bar and bounced to safety.
While Madrid can celebrate a spot in the next round of the Champions League, Malmo's defeat to Shakhtar ensures that PSG are just one win away from joining the Spanish side in advancing.
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