One-dimensional TiO 2 array grown on optically transparent electrode holds a promise as a photoelectrode for photoelectrochemical water splitting; however, its crystal structure is rutile, imposing constraints on the potent use of this nanostructure. To address this issue, a heterojunction with type-II band alignment was fabricated using atomic layer deposition (ALD) technique. One-dimensional core/shell structured TiO 2 /ZnO heterojunction was superior to TiO 2 in the photoelectrochemical water splitting because of better charge separation and more favorable Fermi level. The heterojunction also possesses better light scattering property, which turned out to be beneficial even for improving the photoelectrochemical performance of semiconductor-sensitized solar cell.