Nicolas made her debut on the French national team in 1995. Until her retirement from the national team in 2008 (after the Summer Olympics), Valérie Nicolas played 234 international matches. In 1997 she finishted 10th at the World Championship. She won a silver medal at the 1999 World Championship, after a final match between France and Norway in Lillehammer, which needed two overtimes to break the tie, ending 25-24 to Norway. In 2000, she finished 6th at the Olympics in Sydney, and 5th at the European Championship. She finished fifth at the 2001 World Championship with the French team, and won a bronze medal at the 2002 European Women's Handball Championship. She won a gold medal with the French team at the 2003 World Championship, and was voted Most Valuable Player and All-Star Team goalkeeper at the championship. At the 2004 Summer Olympics in Athens she finished fourth with the national team. She finished 12th at the 2005 World Championship in Russia, and won a bronze medal at the 2006 European Women's Handball Championship. At the 2007 World Championship in France, where the French team placed fifth, her performance was recognized again, and she was selected a member of the All-Star Team together with her Ikast teammates Gro Hammerseng and Katja Nyberg. She competed at the 2008 Summer Olympics in Beijing, where the French team finished fifth, and she ranked shared second on the Top Goalkeepers list with a 40% save rate.