The 2005–06 season finished without silverware for Benfica, with Luisão again as an automatic first-choice. However, the team reached the season's UEFA Champions League quarter-finals, with the defender playing all the matches and minutes in the competition. On 21 February 2006, he scored in his side's 1–0 home win against holders Liverpool, which had lost just 1 of 13 European matches the previous year and 5 of 41 away from home. He also started in the second leg, a 2–0 win at Anfield.