The removal of emerging contaminants from water and production of green energy are some of the pressing needs of today's world. The use of water pollutants for the production of H can be a powerful strategy for solving both these problems. Several approaches have been proposed for this purpose, such as photocatalysis, electrocatalysis and photoelectrocatalysis. In this context, TiO is the most commonly used material, but it has several performance limitations. However, they can be improved with appropriate surface modifications. In this work, the inner surfaces of nanostructured TiO-based films were modified to improve their photoelectrocatalytic and photocatalytic performances, with an aim to simultaneously remove a water pollutant (rhodamine B dye) and generate H in a custom-designed dual-chamber reactor. For this purpose, the TiO nanostructure, which can be used as a photoanode in photocatalytic and photoelectrocatalytic experiments, was functionalized by introducing a zirconium phosphate monolayer (ZP modification). The excellent performances of the ZP-modified photoanodes in simultaneously achieving photoelectrocatalytic dye removal and H evolution indicate that they are interesting candidates for attaining sustainable and circular solutions for environmental protection.