We have fabricated epitaxial chalcopyrite alloys with varying compositions and thicknesses on GaAs (001) substrates using a simple physical vapor deposition method. Growth of the films was characterized with Raman spectroscopy as well as by other analytical techniques. We identified both CuInSe2 (001) and CuIn3Se5 (001). All of the spectra were dominated by the A(1)(Gamma(1)((1)) [W-1]) non-polar optical made at 172 cm(-1) for CuInSe2 and 152 cm(-1) for the CuIn3Se5 phase. In addition, Raman spectra for the thinner layers indicated that these films are under compressive stress due to the lattice mismatch between the films and the substrate.