Direct water electrolysis was achieved with a novel monolithic photoelectrochemical cell. Bipolar WO3/Pt and dye-sensitized TiO2/Pt semiconductor panels, capable of vectorial electron transfer, have been used for water splitting to yield hydrogen and oxygen; light is the only energy input. The hydrogen production efficiency of this tandem cell, based on the short-circuit current, was similar to 1.9% and the maximum hydrogen production efficiency was similar to 2.5% when 0.2 V positive bias was applied. When a concentrated LiCl aqueous solution was used as an electrolyte, valuable chlorine was obtained instead of oxygen. The maximum yielding efficiency of hydrogen and chlorine was similar to 1.8%.