We report on the development of tungsten-oxide-based photoelectrochemical (PEC) water-splitting electrodes using surface modification techniques. The effect of molybdenum incorporation into the WO3 bulk or the surface region of the film is discussed. Our data indicate that Mo incorporation in the entire film (WO3:Mo) results in poor PEC performances, most likely due to defects that trap photo-generated charge carriers. However, compared to a pure WO3 (WO3:Mo)-based PEC electrode, a 20% (100%) increase of the photocurrent density at 1.6 V vs. SCE is observed if the Mo incorporation is limited to the near-surface region of the WO3 film. The resulting WO3:Mo/WO3 bilayer structure is formed by epitaxial growth of the WO3:Mo top layer on the WO3 bottom layer, which allows an optimization of the electronic structure induced by Mo incorporation while maintaining good crystallographic properties.