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Heterostructured TiO2 nanorod@nanobowl (NR@NB) arrays consisting of rutile TiO2 nanorods grown on the inner surface of arrayed anatase TiO2 nanobowls are designed and fabricated as a new type of photoanodes for photoelectrochemical (PEC) water splitting. The unique heterostructures with a hierarchical architecture are readily fabricated by interfacial nanosphere lithography followed by hydrothermal growth. Owing to the two-dimensionally arrayed structure of anatase nanobowls and the nearly radial alignment of rutile nanorods, the TiO2 NR@NB arrays provide multiple scattering centers and hence exhibit an enhanced light harvesting ability. Meanwhile, the large surface area of the NR@NB arrays enhances the contact with the electrolyte while the nanorods offer direct pathways for fast electron transfer. Moreover, the rutile/anatase phase junction in the NR@NB heterostructure improves charge separation because of the facilitated electron transfer. Accordingly, the PEC measurements of the TiO2 NR@NB arrays on the fluoride-doped tin oxide (FTO) substrate show significantly enhanced photocatalytic properties for water splitting. Under AM1.5G solar light irradiation, the unmodified TiO2 NR@NB array photoelectrode yields a photocurrent density of 1.24 mA cm(-2) at 1.23 V with respect to the reversible hydrogen electrode, which is almost two times higher than that of the TiO2 nanorods grown directly on the FTO substrate.