Vanadium pentoxide coatings were grown by atmospheric pressure chemical vapor deposition varying the gas precursor ratio (vanadium (IV) chloride:water) and the substrate temperature. All samples were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, cyclic voltammetry, and transmittance measurements. The water flow rate was found to affect the crystallinity and the morphological characteristics of vanadium pentoxide. Dense stacks of long grains of crystalline oxide are formed at the highest amount of water utilized for a substrate temperature of 450 • C. Accordingly, it was indicated that for higher temperatures and a constant gas precursor ratio of 1:7, the surface morphology becomes flattened, and columnar grains of uniform size and shape are indicated, keeping the high crystalline quality of the material. Hence, it was possible to define a frame of operating parameters wherein single-phase vanadium pentoxide may be reliably expected, including a gas precursor ratio of 1:7 with a substrate temperature of >450 • C. The as-grown vanadium pentoxide at 550 • C for a gas precursor ratio of 1:7 presented the best electrochemical performance, including a diffusion coefficient of 9.19 × 10 −11 cm 2 ·s −1 , a charge density of 3.1 mC·cm −2 , and a coloration efficiency of 336 cm 2 ·C −1 . One may then say that this route can be important for the growth of large-scale electrodes with good performance for electrochromic devices.