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The substitutional sites of Co 2+ ions in Co 2+ -doped CuG 1-x Al x Se 2 (including CuGaSe 2 where x=0 and CuAlSe 2 where x=1) semiconductors are studied by analyzing the composition x dependence of optical spectral parameters reported in the previous literature for these materials. From the studies, we suggest that Co 2+ occupy I-group cation site rather than III-group cation site. The suggestion is discussed.