Albiol returned the following season to the Mestalla Stadium, and quickly established himself as first-choice due to his versatility. In the opening game of the 2006–07's league campaign he scored the winner (his only goal of the season) against Real Betis in a 2–1 home win. He also netted from long distance against Olympiacos F.C. on 12 September 2006, in that year's UEFA Champions League, which Valencia won 4–2 away; during his four-season spell with the first team, his smallest output consisted of 29 games, and he helped the "Che" to the 2007–08 edition of the Copa del Rey.