Luis Suarez has become the first player to score a penalty in El Clasico other than Lionel Messi or Cristiano Ronaldo since May 7, 2008.
The Uruguay international has come under fire for his form this season but added the second goal for Barca from the spot after 30 minutes.
He won the kick himself as he attempted to reach a cross but was bundled over in the box by Raphael Varane, and after the kick was awarded following a VAR decision, the forward fired low into the right corner of the net from 12 yards, beating Thibaut Courtois, who had dived in the correct direction.
In converting the effort, he claimed the distinction of becoming the first player in over a decade to score a Clasico penalty other than the Ballon d’Or-winning duo.
The last player other than Messi and Ronaldo to score such a goal in the fixture was former Manchester United forward Ruud van Nistelrooy, nearly 10-and-a-half years ago.
Remarkably, the last Barca player to convert an effort in the historic fixture was Ronaldinho back in 2006.
Since then, Samuel Eto'o has missed once, but Messi had taken six in succession for the Camp Nou side. Despite his reputation for being uncertain from the spot, the Argentine converted all of those he took.
Ronaldo, meanwhile, has taken four, netting with each one.
Indeed, Eto'o's unsuccessful effort in December 2008 remains the last in which a player has failed.
The latest fixture is the first Clasico in over a decade in which neither Messi nor Ronaldo has featured, and their dominance of the rivalry is highlighted by this incredible penalty statistic.
Barcelona had earlier taken the lead via Philippe Coutinho, who rounded off a lengthy move that involved 30 passes before he slotted low into the net to give the Catalans the lead at Camp Nou.
Marcelo got one back for Los Blancos early in the second half, but Suarez then scored a bullet header and deft chip as he scored the 25th hat-trick in Clasico history on what was a memorable evening for the ex-Liverpool man.