This work demonstrates the ability of nanoporous carbons to boost the photoelectrochemical activity of hexagonal and monoclinic WO3 towards water oxidation under irradiation. The impact of the carbonaceous phase was strongly dependent on the crystalline structure and morphology of the semiconductor, substantially increasing the activity of WO3 rods with hexagonal phase. The incorporation of increasing amounts of a nanoporous carbon of low functionalization to the WO3 electrodes improved the quantum yield of the reaction and also affected the dynamics of the charge transport, creating a percolation path for the majority carriers. The nanoporous carbon promotes the delocalization of the charge carriers through the graphitic layers. We discuss the incorporation of nanoporous carbons as an interesting strategy for improving the photoelectrochemical performance of nanostructured semiconductor photoelectrodes featuring hindered carrier transport.