In this research, a photocatalyst is prepared by pulse-electrodeposition of ZnSe nanoparticles of 2.7 eV bandgap onto the surface of TiO2 nanotube array films. Under AM 1.5G illumination the ZnSe sensitized TiO2 nanotube arrays (ZnSe/TiO2 NTAs) exhibit a significantly increased capability for photocatalytic degradation of pentachlorophenol with support of photo-Fenton system (Fe3+/H2O2/humic acid) which is investigated as oxidants. After 2 h illumination 99.0% of pentachlorophenol is removed, compared to 64.0% using the non-sensitized TiO2 NTAs. The studied concentration of Fe3+, H2O2, humic acid in photo-Fenton system were 100 mu M Fe3+, 75 mu M H2O2, 220 mu M, respectively. The initial concentration and stability were investigated to be important factors that influence the photocatalytic degradation and catalytic ability. (C) 2013 Elsevier B.V. All rights reserved.