The influence of varying relative humidity (RH∼55 and 75%) during thin film deposition from an oxalato-acetylated peroxotungstic acid sol by dip coating, on the microstructure and electrochromic properties of pristine tungsten oxide (WO3) films obtained upon annealing is presented. The films fabricated under a relative humidity of 55% are amorphous whereas the ones cast under a substantially humid atmosphere (RH∼75%) are characterized by interconnected nanocrystallites with a triclinic phase and a nanoporous surface morphology as well. Upon lithium insertion, larger integrated values of transmission modulation and coloration efficiency are observed over the photopic and solar regions, for the films prepared under a RH∼75% as compared to that observed for the films deposited under a RH of 55%. Functional improvements are due to the larger surface area of nanocrystallites and a porous microstructure, a consequence of a higher degree of hydration and hydroxylation in the former films in contrast to the non-porous and a rather featureless structure of the latter films. Faster switching kinetics between the clear and blue states, a greater current density for lithium intercalation, a higher diffusion coefficient for lithium and a superior cycling stability, again shown by the film fabricated under a 75% RH confirm that the WO3 film microstructure is most conducive for a more facile ion insertion-extraction process, which hints at its potential for electrochromic window applications. © 2006 Elsevier B.V. All rights reserved.