Nanostructured iron oxide thin films have been prepared by electrodeposition technique and annealed at various temperatures. The effect of deposition potential, deposition time and annealing temperature on photoelectrochemical (PEC) properties of α-Fe2O3 thin films was studied. The (1 0 4) and (1 1 0) peak presence in X-ray diffraction patterns confirms α-Fe2O3 phase formation. The transition on surface morphology from nanosheets to elongated dumbbell shaped nanoparticles occurred that can be attributed to annealing temperature varied from 400 to 700 °C. Optical band gap variation was observed due to annealing temperature. It was found that increment in film thickness increases the photocurrent from 253 μA/cm2 to 488 μA/cm2 at 0.4 V vs Ag/AgCl.