Fabian Ruiz gave Spain the lead before Charles De Ketelaere equalized for Belgium late in the first half. With extra time looming, Merino came off the bench to score in the 88th minute, sealing Spain’s place in the last four.
Spain dominated possession from the opening whistle but initially struggled to break through Belgium’s compact defense.
Lamine Yamal provided the first signs of danger, repeatedly taking on defenders and earning a series of free kicks, while Belgium relied on counterattacks through Jeremy Doku and Leandro Trossard.
Spain finally found the breakthrough in the 30th minute. Yamal raced down the right and squared the ball for Dani Olmo, whose shot was saved by Thibaut Courtois. Ruiz reacted quickest to tap home the rebound after escaping his marker.
Belgium made the most of their limited opportunities and leveled in the 41st minute.
Kevin De Bruyne released Timothy Castagne down the right, and his early cross was headed into the net by Charles De Ketelaere after he beat Pau Cubarsi in the air.
The first half ended 1-1 despite Spain enjoying the majority of possession and chances.
Spain resumed with greater urgency after the break.
Yamal, Olmo and Mikel Oyarzabal all tested Courtois, who produced several important saves to keep Belgium level.
Belgium responded by introducing Romelu Lukaku, Axel Witsel and Joaquin Seys just after the hour mark, while Spain sent on Pedri and Ferran Torres in search of a winner.
The match took another turn when Courtois suffered a thigh injury after the second-half cooling break. The veteran goalkeeper was unable to continue and was replaced by Senne Lammens in the 70th minute.
Spain continued to press, with Pedri and Nico Williams combining down the left after the latter came on as a substitute.
Coach Luis de la Fuente introduced Merino in the 86th minute, and the midfielder made an immediate impact.
Two minutes later, Cubarsi’s long-range effort was spilled by Lammens, allowing Merino to react first and convert from close range for his second decisive late goal of the knockout stage after also scoring the winner against Portugal in the round of 16.
Belgium nearly found another equalizer in stoppage time when Alexis Saelemaekers dribbled past goalkeeper Unai Simon and crossed into the box, but Cubarsi recovered to clear the danger.
Spain held on through seven minutes of added time to secure a semifinal place against France.
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