In this paper, we report the preparation of visible-light active direct Z-scheme Cu2O/WO3 nanocomposite photocatalyst by a solid-state reaction avoiding the otherwise inevitable formation of CuWO4 phase in wet syntheses. Structure, morphology, and thermal and optical properties of prepared WO3 nanoplatelets decorated by Cu2O were investigated by XRD, Raman spectroscopy, SEM/TEM, combined thermogravimetric (TG)/differential scanning calorimetry (DSC) analysis, and UV–VIS spectroscopy. The photocatalytic performance of the prepared samples under UV and visible light was studied through monitoring discoloration of methylene blue under illumination by selected wavelengths, allowing for the distinguishing between the contributions of the two semiconductive components. Experimental results showed that the decoration of WO3 nanoplates by Cu2O nanoparticles led to an improvement in photocatalytic performance, regardless of used LED (Light-Emitting Diode) wavelength, even at low concentrations. By using scavengers selectively blocking reactive species involved in the discoloration reaction, we determined that the Cu2O/WO3 nanocomposite exhibited the characteristics of direct Z-scheme-type photocatalyst.