Thin films of CdSe grown by non-catalytic displacement plating (NCDP) are characterised electrochemically and photoelectrochemically in polysulphide electrolyte; using Cyclic Voltammetry in dark and under intermittent illumination, band edges of NCDR-plated CdSe are located. A depletion width of 2 μm is calculated across the CdSe/S 2 - /S 2 2 - interface. Charge transfer mechanism across this junction is dicussed. Electrochemical and photoelectrochemical stabilities of NCDP-plated CdSe electrode are studied. Efficiency and fill factor of as-fabricated photoelectrochemical (PEG) cell are found to be 1.02% and 0.34, respectively.