Thin films of CdSe and Fe-doped CdSe (Fe:CdSe) were deposited onto stainless steel substrates by electrodeposition technique. The photoelectrochemical investigations have been carried out using the cell configurations CdSe/1 M (Na2S-S-NaOH)/C and Fe:CdSe/1 M (Na2S-S-NaOH)/C for studying the current-voltage (I-V) characteristics in dark and under illumination, photovoltaic output, spectral response, photovoltaic rise and decay characteristics. The studies reveal that films are n-type conductivity. The junction quality factor in light (n(1)), series and shunt resistance (R-s and R-sh), fill factor (FF) and efficiency (eta) for the cell have been estimated. After Fe doping, efficiency and FF of PEC solar cell is found to be improved from 0.34% and 31.12 to 1.80% and 35.78, respectively. (c) 2007 Elsevier B.V. All rights reserved.