Herein, we report a surface modified TiO₂ nanowire arrays (NAs) photoanode based photocatalytic fuel cell (PFC) towards simultaneous enhancement of actual wastewater treatment and electricity generation under visible light irradiation. TiO₂ NAs were facile fabricated via two-step anodization process in ethylene glycol and glycerin solution, respectively. Actual wastewater samples were directly applied to evaluate the PFC performance in terms of wastewater degradation and electricity generation through the as-prepared TiO₂ NAs photoanode without loading noble-metals or semiconductors. TiO₂ NAs photoanode prepared from ethylene glycol solution demonstrated a highly ordered surface network, exhibiting short-circuit current density and fill factor nearly 4.3 times and 1.4 times higher than pristine TiO₂ NAs photoanode prepared according to previous reports. The experimental results revealed that the fabrication of TiO₂ NAs by a facile surface modification in ethylene glycol solution can be considered a low-cost and scalable routine for enhancing performance of PFC photoanode towards efficient actual wastewater treatment and electricity generation.