text: Photoelectrochemical devices for conversion of solar energy into both electrical energy and chemical energy are discussed with emphasis on how the various material properties of the photoactive electrodes influence device efficiency and stability. The similarity between photoelectrochemical cells (PECs) and solid state devices is used to model their behaviour and optimize such parameters as band gap, doping level, minority carrier lifetime, etc. A model is presented which calculates the electron affinity of any semiconductor and allows the prediction of the open circuit voltage of wet photovoltaic cells and optimum biasing forchemical producing cells. The effects of absorbed ions at the semiconductor/electrolyte interface are reviewed. The temperature dependence of the energy levels in the semiconductor and the electrolyte are considered and the implications of these results to operation of PECs at elevated temperature are discussed. The major differences between PECs and solid state devices are the stability considerations.