Owing to its excellent chemical stability and low cost, titanium dioxide (TiO2) has been widely studied as a photoanode for photoelectrochemical (PEC) water splitting. However, TiO2's practical applications in solar energy-to-synthetic fuel conversion processes have been constrained by its inherently poor ability to transport photogenerated electrons and holes. In this paper, we report Ta-doped porous TiO2 nanorod arrays on Ta foil (Ta-PTNA) that do not possess this issue and that can thus efficiently photoelectrocatalyze water oxidation, helping the production of H2 (a clean fuel) from water at the expense of solar light. The materials are synthesized by a new, facile synthetic approach involving the hydrothermal treatment of a TiO2 precursor with Ta foil, without seeds and templates, and followed by calcination of the product. Besides serving as a source of Ta dopant atoms, Ta foil is found to play a vital role in the formation of nanopores in the materials. The material obtained with hydrothermal treatment at 180 °C for 10 h (Ta-PTNA-10), in particular, affords very large photocurrent density and very high photoconversion efficiency (0.32% at 0.79 V vs. RHE, which is better than those of many previously reported photocatalysts and ∼4 times larger than that of undoped TiO2 nanorod arrays). Ta-PTNAs' remarkable PEC catalytic performance is found to be due to their nanoporous structure and high electronic conductivity.