Titanium dioxide (TiO2) nanotube arrays (TNAs) decorated with antimony selenide (Sb2Se3) particles were successfully fabricated through a simple and efficient electrodeposition strategy, which exhibited excellent catalytic performance for the reduction of p-nitrophenol. The electrodeposition mechanism was investigated by electrochemical methods. The microstructure, chemical composition and morphologies of the Sb2Se3/TNAs prepared at different deposition potentials were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The formation of Sb2Se3 was confirmed to follow a co-deposition mechanism. It was found that Sb2Se3/TNAs with homogeneous morphology could be obtained at −0.7 V, which exhibited the highest catalytic performance for the reduction of p-nitrophenol to p-aminophenol. The conversion rate of p-nitrophenol reached as high as 93.5% within 80 min. Such good catalytic performance could be attributed to the large surface area of TNAs that facilitate electrodeposition of Sb2Se3 and hence improve its catalytic performance.