Pokou was a member of the Ivorian national team, who was twice the highest goalscorer of the Africa Cup of Nations, scoring six goals in the 1968 tournament in Ethiopia and eight in the 1970 edition in Sudan, including 5 in one match against Ethiopia, which Ivory Coast won 6–1. This performance gave him his nickname "L'homme d'Asmara" (the man of Asmara). With 14 total goals, he is also the tournament's second highest overall goalscorer, behind Cameroon's Samuel Eto'o, who eclipsed Pokou's record in the 2008 ACN tournament.