Two alternative crystal structures have been identified in evaporated films grown from synthesized CuInSe2. The first one, tetragonal CuInSe2 was obtained by 'flash' evaporation and the second one, the ordered vacancy compound CuIn2Se3.5 by e-beam evaporation. They had optical gaps of 1.0 for the first and 1.24 eV for the second. The conductivities were p- and n-type, respectively; the last one remained n-type even after annealing in selenium atmospheres. The combination of both films in the heterostructure Mo/CuInSe2/CuIn2Se3.5/CdS/ITO has been obtained and is at present being studied as a solar cell.