CuxGaySe2 MOCVD and PVD grown films were structurally and optically characterized by Raman, Micro-Raman and photoluminescence spectroscopy. Defect related photoluminescence excitation with wavelengths varying across the material band gap reveals: a) in Cu-rich CuGaSe2 films, three band edge splitting due to the spin-orbit interaction and the crystal field, and donor-acceptor pair recombination between a shallow donor and two different acceptor levels, and b) in Ga-rich CuGaSe2 films, donor-acceptor pair transitions between quasi-continua of donor and acceptor levels related to potential fluctuations. Raman spectra of CuxGaySe2films, excited by laser light near and below the material band gap, show intense modes at 197cm-1, 187cm-1, and 277cm-1, which can be used as indicators of crystallinity and Ga-content of the films. Polarization- and angular- dependent micro-Raman spectra of MOCVD CuGaSe2 indicate that CuxSey-crystallites, dispersed on the surface of Cu-rich films, are grown oriented with their c-axis perpendicular to the film surface.