A photoelectrochemical (PEC) cell composed of two semiconductor electrodes, a photocathode, and a photoanode is a potentially effective means of obtaining hydrogen through spontaneous overall water splitting under light irradiation. However, the long-term stability (that is, operation for more than one day) of a PEC cell has not yet been demonstrated. In addition to the corrosion of both photoelectrodes, the gradual migration of heavy metal cations from the photoanode into the electrolyte can also result in degradation of the cell by contamination of the photocathode surface. In the present work, BiVO4-based photoanodes were used in conjunction with two different modifications: dispersion of a chelating resin in the electrolyte and coating of the photoanode surface with an anion-conducting ionomer. The chelating resin was found to capture Bi3+ cations in the electrolyte before they became deposited on the cathode surface. Consequently, a PEC cell incorporating a BiVO4-based photoanode and a (ZnSe)0.85(CuIn0.7Ga0.3Se2)0.15-based photocathode showed stable overall water splitting over a span of two days under simulated sunlight. To the best of our knowledge, this represents the longest period over which stable PEC cell performance has been established. A considerable decrease in the performance of the BiVO4-based photoanode was still observed due to the continuous dissolution of Bi species, but surface coating of the photoanode with an anion-conducting ionomer prevented the movement of Bi3+ ions into the electrolyte because of the selective conduction of ions. The coating also served as a protective layer that improved the durability of the photoanode. This study therefore suggests a simple yet effective method for the construction of stable PEC cells using semiconductor photoelectrodes.