This study evaluated the application of a membrane-free photocatalytic fuel cell composed of a TiO2 nanotube array photoanode and a Cu cathode, i.e. TNA-Cu PFC system, for micropollutant removal from water. Significantly enhanced removal of a commonly present aqueous micropollutant 4-chloro-2-methylphenoxyacetic acid (MCPA) was obtained in this TNA-Cu PFC system: the TNA-Cu PFC system achieved better MCPA degradation compared to the conventional photocatalytic method using the same catalyst. In the TNA-Cu PFC system, the MCPA degradation was largely promoted under acidic conditions, indicating this as an important operational condition. The enhancement of MCPA degradation in the TNA-Cu PFC system involved better e(-)/h(+) separation and generation of other oxidants: in conventional photocatalytic process, hydroxyl radicals in liquid phase contributed to 93.7% MCPA degradation while only 2.4% MCPA degradation was mediated by other oxidants like O-center dot(2)-, H2O2, (HO2)-H-center dot; for MCPA degradation in the TNA-Cu PFC system, the contribution of hydroxyl radicals in the liquid phase decreased to 83.6%, while contribution of other oxidants like O-center dot(2)-, H2O2, (HO2)-H-center dot increased to 15.3%. This change in MCPA degradation mechanisms was confirmed via degradation intermediates analysis by LC-MS/MS. The study on the effect of electrolyte concentration suggests that when operated under acidic conditions, addition of electrolyte is not required. The TNA-Cu PFC system was shown to work well in the presence of up to 15 mg/L natural organic matter (originating from two large rivers), high amounts of common inorganic ions, and even in WWTP effluent. The TNA-Cu PFC system also exhibited relatively good stability after several cycles of repeated use. The obtained results demonstrated that this is an adequate system for micropollutant removal from water at various places in the water cycle, i.e. as polisher of WWTP effluents before discharge or for cleaning intake water before producing drinking water.