The properties of ZnSe/PEO junction photoelectrochemical cells have been studied under dark and illuminated conditions. ZnSe was electrodeposited onto an indium tin oxide (ITO) glass and the polymer film of PEO-chitosan: NH4I (+I-2) was placed over it followed by another ITO glass. The polymer film was prepared by the solution cast technique. The open circuit voltage (V-oc) of the fabricated cells was between 300 mV to 400 mV. In the dark the device operates as a diode while under illumination it operates as a photoelectrochemical cell.