Photocatalytic water-splitting accompanied by dihydrogen evolution has been observed when S x 2− ( x = 1, 2, 3 …) was used as the anolyte, n-CdSe as the semiconductor (SC) electrode and platinized-Pt as the cathode. Best results were obtained when the semiconductor electrode was prepared by depositing a thin film of CdSe by the RF-sputtering technique on a stainless steel substrate. An attempt has been made to develop a device as a model rechargeable solar electrosynthetic cell.