Defour scored once in three appearances in qualification for the 2014 World Cup, opening a 2–0 win away to Scotland on 6 September 2013. He was selected for the finals in Brazil by manager Marc Wilmots, making his debut in the competition on 26 June in the third group stage match against South Korea after Belgium had already won their first two outings and sealed qualification, and was sent off in the last minute of the first half of the eventual 1–0 success after a rash tackle on Kim Shin-wook.