In this work, we present the optoelectronic characterization of pure tungsten oxide nanoparticle networks synthesized and self-assembled by flame spray pyrolysis. Current-voltage measurements performed in dark conditions indicate the presence of trapping and de-trapping phenomena from defects inside the energy gap. The presence of defects is confirmed by the time evolution of the photocurrent, measured under monochromatic radiation at 420 nm. After illuminating the WO3 films with light, the current increases exponentially with a time constant independent on the applied voltage. This behavior is ascribed to the presence of defects lying at 1.1 eV below the conduction band of WO3 (bandgap of ca. 2.9 eV). When the illumination is terminated, the photocurrent shows an exponential decrease, once again independently on the applied voltage. The defect level corresponding to this relaxation process corresponds to 0.92eV below the conduction band.