On 6 September 2006, Klose scored two away goals against San Marino in a 13–0 Euro 2008 Qualifying win which took his international goal tally to 33, the same amount as his idol Fritz Walter and to joint 7th in the list of all-time goalscorers for Germany.He had a goal drought for a long time with the national team, causing speculation that he may be dropped from the starting line-up. But German coach Joachim Löw has denied this.
Another highlight in Klose's career came on 8 September 2007, as he captained Germany for the first time and celebrated this honour by scoring both of his country's goals in a 2–0 victory over Wales. The next day, one of the headlines in the UEFA official website was “Captain Klose Takes Germany Closer (to qualifying).”
In the main tournament, Klose started the opening group game against Poland and assisted Lukas Podolski's two goals in a 2–0 victory. He played the remaining two group games against Croatia and Austria with no goals. He finally broke his duck during the knockout stages, scoring the second goal for Germany during both quarter final and semi-final against Portugal and Turkey. However he was unable to score during the final against Spain.