In this study, SnS decorated TiO2 nano-tube array (SnS/TiO2 NTAs) photoelectrode, which was applied for degradation of 2,4,6-trichlorophenol under simulated visible light illumination, was synthesized by anodization combined with electrodeposition strategy. Afterwards, series of the systematical physicochemical properties were measured. Results show that SnS/TiO2 NTAs photoelectrode exhibited improved visible light range of 650 nm and transient photocurrent density of 0.119 mA cm−2, as well as higher photo-generated charge separation efficiency, because of the synergistic effect between TiO2 and SnS. Also, the enhanced charge separation and photoelectrocatalysis (PEC) mechanism were further confirmed by photoluminescence spectroscopy and visible light assisted PEC efficiency for degradation of 2,4,6-trichlorophenol. It is worth mentioning that SnS/TiO2 NTAs photoelectrode displayed excellent stability and reusability, for the degradation efficiency of repeated experiments were all over 90% after 5 runs. All these results indicated SnS/TiO2 NTAs photoelectrode has great potential for the degradation of organic pollutants in waste water treatment.