At the French Athletics Outdoor Championships held in Angers on 15 July 2005, Doucouré won the 110m hurdles for the second consecutive year in a time of 12.97 s, setting a new national outdoor record and becoming he first French athlete to go under 13 seconds in that event.

At the 2005 World Championships, Doucouré won the 110m hurdles gold medal in a time of 13:07 s, beating 2004 Olympic Champion Liu Xiang by one hundredth of a second and veteran Allen Johnson by three hundredths of a second.

He (together with Ronald Pognon, Eddy De Lépine and Lueyi Dovy) also won the gold medal in the 4×100 metres relay event at the same championships.

The following year, he started strongly by winning the 60 m hurdles gold medal at the 2009 European Indoor Championships.

At the 2012 Olympics in London, he finished last in his semi-final heat of the 110m hurdles – the only event that he entered – and thus did not qualify for the final.