Electrochemical synthesis of tungsten oxide (WO3) thin film nanostructures by potentiostatically controlling the surface aggregates formed at the electrode-electrolyte interface, in the presence of a polymeric template (polyethylene glycol 400, PEG) from a plating sol of peroxotungstic acid (PTA) is presented. The nanoparticulate morphology of the WO3 film changes drastically upon varying PEG content in the precursor sol; from an amorphous structure with randomly distributed pores for a film derived from a PTA sol with PEG:ethanol in a 3:7 volume ratio, to a mesoporous, nanocrystalline material with hybrid structures encompassing spherical grains and nanorod-like shapes with a triclinic modification for a film formed in a sol with PEG:ethanol in a 1:1 volume ratio. This approach highlights the role of the PEG proportion in controlling crystal growth, assembly patterns and pore structure. The film derived from the sol with PEG:ethanol in a 1:1 volume ratio exhibits superior transmission modulation and coloration efficiency as compared to the film obtained from a sol with PEG:ethanol in a 3:7 volume ratio. While the latter film deteriorates rapidly within 35 color-bleach cycles, the former film sustains more than 3500 cycles, without significant degradation. This film also exhibits fast switching between the clear and blue states; these are repercussions of the mesopore structure and the interconnected nanocrystallite phase. © 2007 Elsevier B.V. All rights reserved.