WO/sub 3/ films prepared under different conditions (evaporation, reactive sputtering and spraying of aqueous solutions of metatungstic acid) differ by orders of magnitude in their electrochromic sensitivity. Diffuse X-ray studies show the evaporated and sputtered films to be amorphous and to consists of a disordered network of corner sharing WO/sub 6/ octahedra. Sprayed films have different degrees of crystallinity depending on spraying conditions. From differential scanning calorimetry we conclude that the crystal water present in most films strongly affects the local order of the corner sharing octahedra. We find that crystal water not only provides a high ionic conductivity which is conditional for a fast electrochromic reaction but also stabilises electrocatalytically active surface sites for fast hydrogen or Li exchange with the adjacent electrolyte.