Zinc oxide (ZnO) and niobium oxide (NbO x ) with a nano-island structure were deposited by a sputtering method on Al-coated glass substrates. Cells with a (ZnO or NbO x )/Al/glass|KNO 3 aq.|Al/ glass structure were assembled, and electrochemical and photoelectrochemical properties were evaluated. The ZnO and NbO x electrodes had higher electrode potentials than the counter Al/glass electrode, and electron flows from the counter electrode to the ZnO and NbO x electrodes through the external circuit were commonly confirmed. In the ZnO-based cell, only faint photocurrent generation was seen, where Zn and Al elution from the ZnO electrode was found. In the NbO xbased cell, however, stable generation of electricity was successfully achieved, and electrode corrosion was not recognized even in microscopic observations. A photoelectrochemical conversion model was proposed based on potential-pH diagrams. In the case of nano-island structures formed at shorter NbO x deposition time, it was concluded that the photoelectrochemical reactions, which were proceeded in the immediate vicinity of the boundary among nano-islands, substrate, and electrolyte solution, were predominant for the photoelectrochemical conversion, and in the case of film structures with longer deposition time, the predominant reactions took place at the film surface.