During Italy's closely fought 1–0 over Australia in the round of 16, Zambrotta received a booking in the 91st minute. In the quarter-final on 30 June, Italy defeated Ukraine 3–0, with Zambrotta scoring the opening goal after six minutes with a left-footed long-range shot after a one-two with Francesco Totti. This was his second goal for his country. Zambrotta's outstanding performance continued as he saved his team by a goal-line clearance in the 58th minute. After Lippi made some substitutions, Zambrotta was pushed up to a left midfield position. He immediately showed the effect of this position switch. In the 69th minute, he dribbled down the left flank into the edge of the penalty area and passed the ball across to Luca Toni to score his second goal of the match.