Rikke Skov made her debut with the national team on 28 July 2000, and was appointed team captain in 2007. She received an Olympic gold medal in Athens 2004 and a silver medal at the 2004 European Championship. Skov first retired from international handball in April 2009, until when she played 107 matches and scored 296 goals. However, Skov later changed her mind and participated on the 2010 European Women's Handball Championship, where she reached the fourth place. In 2011, she continued to play for the national team and participated among others on the GF World Cup '11, but before the squad selection for the 2011 World Championship she withdrew from the team to focus fully on her club duties. On Friday 29 April she announced that she ended her national team career.