Nick Kyrgios' participation in the Valencia Open was brought to a swift end as qualifier Daniel Brands claimed a shock three-set victory.
Brands is 140 places below Kyrgios in the world rankings, but it was the German who held his nerve in a deciding tie-break and set up a second-round meeting with top seed David Ferrer - a three-time champion at this event.
Kyrgios gave up a 3-0 lead in the first set, but then reeled off four games in succession to win the second.
There were to be no more breaks after that and, having twice held to love at the end of the third set, Brands came through the breaker to win 6-4 2-6 7-6 (7-3).
Fernando Verdasco was the champion in Valencia 11 years ago, but joined Kyrgios in making a first-round exit this time around as he lost to sixth seed Guillermo Garcia-Lopez.
The day's final match saw Garcia-Lopez, who had lost his last five meetings with fellow Spaniard Verdasco, triumph 6-4 3-6 6-3.
Benoit Paire, the fifth seed, came from a set down to beat lucky loser Norbert Gombos 3-6 6-3 6-4, but another Frenchman, Jeremy Chardy, suffered contrasting fortunes as Aljaz Bedene beat him 3-6 6-2 6-1.
Bedene's serving was particularly impressive as he sent down 14 aces and lost just four first-service points.
Qualifiers Taro Daniel and Mischa Zverev won in three sets against Michal Przysiezny and Thomaz Bellucci respectively, while Joao Sousa claimed a 7-6 (11-9) 6-3 victory over Gilles Muller.