Zn1-xCdxGa2Se4 crystals and Co2+-doped ones with values between x = 0.0 and x = 1.0 at intervals of 0.2 were investigated by XRD and Raman spectroscopy in order to determine the possible site of CO2+ ions in these crystals. It seems from the changes of the lattice parameters and Raman shifts of these samples that Co2+ ions possibly locate at the site of Ga atoms. Since Co2+ ions will act as acceptors in this case, we can also discuss the valence band offset in Zn1-xCdxGa2Se4/ZnGa2Se4 heterojunctions.