A dense array of vertically aligned ZnO-ZnGa(2)O(4) core-shell nanowires was synthesized on a large scale on an a-plane sapphire substrate by a simple two-step chemical vapor deposition method. The ZnO cores and ZnGa(2)O(4) shells of the nanowires are of single crystal quality and have aligned crystallographic orientations as evidenced from XRD and TEM analyses. Mott-Schottky analysis and voltage onset from the photocurrent-voltage curve confirm an n-type semiconductor property, a flat-band potential of -0.4 V (versus NHE) and a carrier density of 7 × 10(18) cm(-3) for the ZnO-ZnGa(2)O(4) core-shell nanowires. A stable and large photocurrent of 1.2 mA cm(-2) was obtained with the ZnO-ZnGa(2)O(4) core-shell nanowire array when used as a photoanode at an applied bias of +0.7 V (versus Ag/AgCl) under a 300 W xenon lamp illumination. Moreover, a low dark current of <10(-4) mA cm(-2) was obtained at an applied bias of +0.7 V (versus Ag/AgCl) without light illumination for the ZnO-ZnGa(2)O(4) nanowire array. These results suggest that the dense array of ZnO-ZnGa(2)O(4) core-shell nanowires provides enhanced electronic properties and stable anti-photocorrosion ability and, therefore, is promising as a photoanode in photoelectrochemical water splitting.