Copper doped‐TiO2 (P25) nanomaterials have been intensively studied as promising catalysts for H2 production by photo‐reforming of selected organic compounds. However, the role of copper oxidation states on the improvement of photocatalytic activity is still debated. In this work, CuOx‐impregnated P25‐TiO2 catalysts were used for photocatalytic production of hydrogen from methanol. Copper species/oxidation states both in the as‐prepared catalysts and after the photocatalytic process were investigated. To this purpose, H2 production rates were correlated to physico‐chemical properties of the samples, both before and after photocatalytic process, by means of Raman, X‐Ray Diffraction, Electron Paramagnetic Resonance spectroscopy, X‐Ray Photoelectron Spectroscopy, Temperature‐Programmed Reduction and High Resolution Transmission Electron Microscope techniques. Results revealed the presence of both Cu2O and CuO deposits on the samples surface after calcination. Notably, under near‐UV irradiation, the fraction of highly dispersed CuO particles undergo a partial dissolution process, followed by reduction to metallic copper Cu(s) by photogenerated electrons, boosting H2 production rate. Our findings indicate that both Cu2O and Cu(s) act as co‐catalysts for H2 generation, yet by different mechanisms. Overall this study, provides the basis to enhance catalytic performance of red‐ox active systems through UV‐irradiation approach.