A photoelectrochemical (PEC) cell includes a photovoltaic electrode that generates voltage under radiation; a solid membrane electrode assembly that includes at least one solid polymer electrolyte and first and second electrodes; a mechanism that collect gases from oxidation and reduction reactions; and an electrical connection between the photovoltaic electrode and the solid membrane electrode assembly. A PEC system and a method of making such PEC cell and PEC system are also disclosed.
 This invention was made with Government support under National Renewable Energy Laboratory (NREL) contract No. NDJ-1-30630-08 awarded by the Department of Energy, and under ARL-WPAFB Grant "Photovoltaic Hydrogen for Portable, On-Demand Power" awarded to the University of Toledo under subcontract 03-S530-0011-01C1 under the primary contract F33615-02-D-2299 through the Universal Technology. The government has certain rights in this invention.