US Open champion Carlos Alcaraz suffered his first straight-sets defeat since November last year as Goffin made the most of his second chance as a lucky loser
Virtual Madrid Open: Andy Murray downed Belgium's David Goffin in the final but the drama of the online tournament took place in the previous round.
World number one Rafael Nadal lost to Belgium's David Goffin in a rare defeat.
Roger Federer plays Alexander Zverev after the young German beat Andrey Rublev of Russia, 6-0, 7-6 (7/4).
Novak Djokovic won points on 87 percent of his successful first serves and never committed a double fault in the roughly 90-minute contest.
Roger Federer, trying to stretch his men's Grand Slam record title total to 21, advanced to a last-eight match up with Bulgaria's 78th-ranked Grigor Dimitrov.
Daniil Medvedev lifted a first Masters 1000 trophy after settling for runner-up finishes to Nick Kyrgios in Washington and Rafael Nadal in Montreal.
Roger Federer secured his 102nd career singles title and remained unbeaten on grass so far this season.
Alexander Zverev served nine double faults in a rollercoaster match, and survived two match points in the third set before ultimately losing in the tiebreaker.
Roger Federer continues his first French Open campaign in four years on Friday with a third-round match against Norway's Casper Ruud, while reigning champion Rafael Nadal faces Belgian David Goffin.