Couto became the first Portuguese player to reach 100 caps (in a total of 110) on 11 October 2003, in a 5–3 friendly defeat of Albania. He was selected as captain for Euro 2004, which was played on home soil, starting in the first game against Greece but eventually being relegated to the bench by Ricardo Carvalho; Portugal went on to reach the final of the tournament, in which the team suffered a defeat against the same opponent.