Molybdenum trioxide (MoO3) thin films prepared by cathodic electrodeposition on indium-tin-oxide coated glass substrates from aqueous peroxo-polymolybdate solutions have been studied as a function of sintering temperature (25-450 degreesC). Cyclic voltammetry, chronopotentiometry, chronoamperometry, and spectroelectrochemical measurements performed with MoO3 thin films in 1 M LiClO4/propylene carbonate demonstrate that the electrochemical behavior (Li+ insertion/extraction and coloration) is strongly dependent upon thermally induced changes in micro-/nanocrystallinity, which directly influence measured Li+ diffusion properties as well as electroinsertion and electrochromic reversibilities. Structural analysis using X-ray photoelectron spectroscopy, X-ray diffraction, and atomic force microscopy indicate that films heat treated at 100 degreesC or less exist as amorphous oxide-hydrates of molybdenum; whereas films heated to 250 degreesC exist as disordered, mixed-phase materials comprising monoclinic beta-MoO3 and orthorhombic alpha-MoO3. Crystallization to the more thermodynamically stable orthorhombic alpha-MoO3 occurs at 350 degreesC and above. The mixed-phase material exhibits inhomogeneous electrochemical activity, evidenced by the existence of complicated voltammetric and chronoamperometric responses. The effects of sintering temperature on ion insertion and electrocoloration properties are discussed.