Fe-57 Mossbauer spectra of well characterized CdTe thin films with substitutions of Fe, In and Sb were recorded and interpreted according to the changes in the ionic radii and electronic properties of these substitutions relative to Cd in the CdTe framework. The literature reports of certain correlations among the iron valence, Fe2+ or Fe3+, and the crystallinity of the films are critically discussed and an explanation of their origin is provided. The Mossbauer results also allow direct understanding of the effect of In and Sb substitutions on the properties of the films.