The oxygen substoichiometry of as-prepared WO3 (tungsten trioxide) nano-powders (NPs) from a polyol process was tuned via peptization of the NPs in aqueous solutions of different Cr2O72− oxidizing concentrations. The as-synthesized materials have been characterized by X-ray scattering (XRD and PDF), transmission electron microscopy (TEM), X-ray photoelectron (XPS), and UV-VIS photochromic activity. The local atomic structure of WO3-X was investigated using total scattering atomic pair distribution function (PDF) analysis based on X-ray total scattering data collected on powder at ambient conditions. The PDF analysis confirms that the crystal structure of all studied samples can be described in terms of very small crystallites with a P21/n space-group monoclinic framework but with anomalous unit cell distortion parameters, indicating that small crystallite sizes resulted in a larger monoclinic distortion (as measured by the beta angle of the unit cell). The nanometer dimension of the crystallites combined as well as the oxygen-tungsten stoichiometric ratio control, are key features for optimized photochromic properties. Moreover, we present the fabrication of a WO3-x thin film based UV photosensor, which was carried out on silica glass substrates via the dip-coating method. The obtained films exhibited a UV photoresponse and photoelectric characteristics at 5 V bias voltages able to detect very low UV doses, inferior to 10 W/m2. The photo-detection measurements prove the usability of our device as a UV photodetector with a good responsivity of 0.37 A/W and external quantum efficiency of more than 100% even at a very low power density (9.2 W/m2) of UV illumination.