CuInSe2 (CIS) thin films have been deposited by MOCVD process, with controlled thickness and composition. Copper precursors based on hexafluoroacetylacetonato copper (Cu(hfa)(2)) have been specially developed. By varying the experimental parameters, a large range of compositions were investigated. Stoichiometric CIS layers present a high absorption in the visible range with an optical bandgap around 1 eV. When moving away from the stoichiometry, the films exhibit a mixture of two phases. The Cu-rich films are composed of Cu2-xSe (x approximate to 0.15) and CIS while on the indium-rich side, the CuIn3Se5 phase is appearing along with CIS. This phase itself has also been obtained and characterized. The different properties of all these films are detailed. The first solar cells, based on CIS grown by MOCVD, have been achieved.