In this paper, we present structural and optical properties of single-phase Cu(In, Ga)(S, Se)2 alloys, which have been prepared using a novel selenization/sulfurization growth process to react copper-indium-gallium alloy films. The grown scheme differs critically from standard two-step grown processes and was carried out without toxic H2S and H2Se gases. The calculated band gap values for layers with varying sulfur content (i.e. S/(S Se) = 0.16 and 0.19), determined from optical transmission and reflectance measurements, were found to be 1.17 and 1.23 eV respectively. The low temperature PL measurements also confirmed the shift in the band gap of the CIGSS absorber films with sulfur incorporation. In summary, this reaction process produced single-phase CIGSS thin films with controlled sulfur amount suitable for photovoltaic application.