Display omitted ► Applications of TiO2 film electrodes in organic pollutants degradation are reviewed. ► TiO2 nanostructured electrodes have shown high efficiency in PEC degradation. ► Influencing factors of PEC degradation of organic pollutants are discussed. ► Improvement of PEC degradation by doped TiO2 film electrodes are demonstrated. ► The kinetic model of PEC degradation of organic pollutants is highlighted. Photoelectrocatalytic (PEC) technology involved applying an electrical bias to a TiO2 film electrode, has been widely applied to the degradation of refractory organic pollutants, owing to its high degradation efficiency. This paper reviews recent developments in the PEC degradation of recalcitrant organic contaminants using a TiO2 film electrode. The preparation and application of various TiO2 film electrodes have been investigated, as well as the parameters that influence PEC activity such as the crystal structure, the film thickness and substrate material, the applied electrical bias, the solution pH and conductivity. The improvement of PEC activity by doping the TiO2 film electrode with metal and non-metal ions has been discussed. The mechanism and kinetics for the PEC degradation of organic pollutants have also been highlighted.