Atrazine, one of the most widespread herbicides in the world, is considered as an environmental estrogen and has potential carcinogenicity. In this study, atrazine was degraded on boron-fluorine co-doped TiO nanotube arrays (B, F-TiO NTAs), which had similar morphology with the pristine TiO NTAs. The structure and morphology of TiO nanotube samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-visible diffuse reflectance spectroscopy (DRS). It showed that the decoration of fluorine and boron made both the absorption in the visible region enhanced and the band edge absorption shifted. The efficiency of atrazine degradation by B, F-TiO NTAs through photoelectrocatalysis was investigated by current, solution pH, and electrolyte concentration, respectively. The atrazine removal rate reached 76% through photoelectrocatalytic reaction by B, F-TiO NTAs, which was 46% higher than that under the photocatalysis process. Moreover, the maximum degradation rate was achieved at pH of 6 in 0.01 M of NaSO electrolyte solution under a current of 0.02 A and visible light for 2 h in the presence of B, F-TiO NTAs. These results showed that B, F-TiO NTAs exhibit remarkable photoelectrocatalytic activity in degradation of atrazine.