Tungsten trioxide (WO₃) is well-known as one of the most promising chromogenic compounds. It has a drastic change of coloration induced from different external stimuli and so its applications are developed as gas sensors, electrochromic panels or photochromic sensors. This paper focuses on the photochromic properties of nanoWO₃, with tunable composition (with tunable oxygen sub-stoichiometry). Three reference samples with yellow, blue and black colors were prepared from polyol synthesis followed by post annealing under air, none post-annealing treatment, or a post-annealing under argon atmosphere. These three samples differ in terms of crystallographic structure (cubic system versus monoclinic system), oxygen vacancy concentration, electronic band diagram with occurrence of free or trapped electrons and their photochromic behavior. Constituting one main finding, it is shown that the photochromic behavior is highly dependent on the compound’s composition/color. Rapid and important change of coloration under UV (ultraviolet) irradiation was evidenced especially on the blue compound, i.e., the photochromic coloring efficiency of this compound in terms of contrast between bleached and colored phase, as the kinetic aspect is high. The photochromism is reversible in a few hours. This hence opens a new window for the use of tungsten oxide as smart photochromic compounds.