Present work reports a photoelectrochemical cell performance of Fe³⁺ doped ZnSe nano particles and hollow spheres. These nanoparticles and hollow spheres are deposited using simple potentiostatic mode of electrodeposition with varying of Fe³⁺ doping percentage. The auxiliary conformations of phase formation through experimental investigation such as XRD, XPS and FT-RAMAN have been done and the results are found consistent with each other. The AFM studies aggress well with FESEM results which eventually confirm formation of nanoparticles. The 0.75% Fe3þ doped ZnSe shows the better photo-electrochemical cell performance due to nanoparticles, relatively less charge transfer resistance, relatively better absorbance, less band gap etc. The observed short circuit current is 175mA and open circuit voltage is 575 mV. The calculated fill factor and efficiency are 0.32 and 21%, respectively for 0.75% Fe³⁺ doped ZnSe. The relatively lower value of series resistance of 0.75% Fe³⁺ doped ZnSe thin film as compared to other deposited films is also responsible for better efficiency of photoelectrochemical cell.