Orange replaces MTN, whose four-year deal expired last year.
A CAF statement on Tuesday said that for the period of the contract, Orange will be title sponsors of CAF's flagship Africa Cup of Nations, the African Nations Championship, the African Youth Championship, the CAF Champions League and the CAF Super Cup.
Additionally, Orange has been given the media broadcast rights for these competitions through mobile rights across 55 countries in Africa.
CAF President Issa Hayatou declared: "Thanks to its technical expertise and renown on the international stage, Orange represents the ideal long- time partner for the development and the image of African football."
Orange is already established as a telecommunications operator in many African countries, and also sponsors the national teams of Côte d'Ivoire, Cameroon, Senegal, Guinea and Botswana.
The deal takes effect from July 28.