The correlation between the temperature-dependent electrochromic (EC) activity and other properties of galvanostatically deposited Prussian Blue (PB) films is presented here. Films subjected to annealing treatment in air at temperatures up to 500°C were characterized by a variety of techniques which include TGA, XRD, FTIR, UV–vis spectrophotometry, SEM, XPS, cyclic voltammetry etc. The as-deposited X-ray amorphous hydrated PB films were blue in color and had Fe in both FeII and FeIII valence states and were electrochromically active. Consequent to changes in the valence state, degree of hydration and coordination environment of the iron ions upon annealing, EC activity and morphology of the films exhibited dramatic changes. Annealing at moderate temperatures retained the blue color of the films and decreased the EC activity consistent with dehydration and decreased the FeII content. Lack of EC activity at higher temperatures was consistent with dehydration and quenching of FeII states accompanied with change of color from blue to rust (FeIII) typical of Fe2O3. Independent of the annealing temperature, the films retained their amorphicity, however, prolonged annealing at 500°C yielded hexagonal Fe2O3.