Nadal, a five-time winner in the Spanish
capital, was the favourite and top seed having lifted the
Barcelona Open trophy last month but played below par on a
sweltering spring day.
Zverev struggled in the opening exchanges, finding himself 4-2
down before breaking Nadal twice to turn the match on its head
and take the first set.
The fifth-seeded German then powered ahead in the second,
breaking Nadal's serve again and holding out to seal a
career-first win on clay against the Spaniard.
He will take on third seed Dominic Thiem in Saturday's
semi-final after the Austrian overcame John Isner 3-6 6-3 6-4.
Later on Friday, Alexander Bublik of Kazakhstan plays fellow
qualifier Casper Ruud from Norway while eighth seed Matteo
Berrettini of Italy faces Chilean 16th seed Cristian Garin.
(Reporting by Joseph Walker; Editing by Ken Ferris)
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