Photoelectrochemical microcell arrays are prepared on the basis of a two-dimensional array of polystyrene microparticles as a template. The microcell array consists of a TiO2 film with bowl-shaped hemispheric voids and gold microcathodes deposited on the brims of the voids. Some microcells are covered with gold domes. Ultraviolet irradiation in an AgNO3 aqueous solution resulted in deposition of silver on the gold brims and domes.