Liquid phase deposition (LPD) technique was employed to prepare α-Fe2O3 films for photoelectrocatalytic degradation of pollutants. The obtained LPD films were characterized by various surface analysis techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS). The results indicated that α-Fe2O3 films with porous structure were successfully deposited on the titanium substrates by the LPD process. The UV–Visible diffuse reflectance spectroscopic (DRS) analysis showed that the obtained LPD α-Fe2O3 film mainly absorbed visible light, which was advantageous to the utilization of solar energy. Under visible light illumination, the Fe2O3 film electrodes exhibited sensitive photocurrent responses, which were affected by the calcination temperature. Consistent with the photocurrent analysis, the α-Fe2O3 film calcined at 600 °C showed the best photoelectrocatalytic performance, and different organic pollutants such as methyl orange (MO) and p-nitrophenol (PNP) were effectively degraded over the LPD film electrode by photoelectrocatalytic treatment under visible light illumination. Display omitted •α-Fe2O3 film is prepared by liquid phase deposition process.•LPD α-Fe2O3 film has a porous structure and absorbs visible light.•Calcination temperature shows a significant effect on the PEC performance of α-Fe2O3 film.•α-Fe2O3 film is efficient for photoelectrocatalytic degradation of pollutants.