A series of Cu2O/TiO2photocatalysts with different molar fraction of Cu2O were prepared by a facilemodified ethanol-induced approach followed by a calcination process. The chemical state of coppercompound was proved to be cuprous oxide by the characterization of X-ray photoelectron spectra (XPS).Furthermore, these composite oxides were characterized by X-ray diffraction (XRD), transmission elec-tron microscopy (TEM), N2adsorption desorption and UV–vis techniques to study the morphologies,structures, and optical properties of the as-prepared samples. The results indicated that the photocat-alytic activity of n-type TiO2was significantly enhanced by combined with p-type Cu2O, due to theefficient p–n heterojunction. The p–n heterojunction between Cu2O and TiO2can enhance visible-lightadsorption, efficiently suppress charge recombination, improve interfacial charge transfer, and especiallyprovide plentiful reaction active sites on the surface of photocatalyst. As a consequence, the prepared 2.5-Cu2O/TiO2photocatalyst exhibited the highest photocatalytic activity for H2evolution rate and reached2048.25 mol/(g h), which is 14.48 times larger than that of pure P25. The apparent quantum yield (AQY)of the 2.5-Cu2O/TiO2sample at 365 nm was estimated to be 4.32%. In addition, the influence of differentscavengers, namely methanol, anhydrous ethanol, ethylene glycol and glycerol, on the photocatalyticactivity for H2evolution rate was discussed.