Spectral photoconductivity, photoconductive quenching, photoluminescence, and thermally stimulated current measurements, have been carried out in order to study the evolution of defect energy levels in CdS thin films, grown in cubic phase by chemical bath deposition, as a function of thermal annealing temperatures in Ar+S-2 atmosphere. The results are influenced by a cubic-to-hexagonal phase transition. From those measurements, a number of trap levels and deep levels in the forbidden band are determined. The results can be explained in terms of the evolution of native and phase transition generated defects in the sample structure.