Ag–AgBr nanospheres were synthesized on the tubular surface of TiO2 nanotube arrays (TiO2 NTA/Ag–AgBr) by the one-pot hydrothermal deposition strategy using cetyltrimethyl ammonium bromide (CTAB) as bromine source and morphology controlling agent. The results showed that the TiO2 NTA/Ag–AgBr (0.025) prepared with 0.025 g CTAB had the uniform particle distribution, high visible light absorption, photoelectric conversion activity and photoelectrocatalytic (PEC) removal of organic dyes and heavy metal ions. The high photocatalytic decomposition of organic pollutants in waste water was attributed to the synergistic effect of Ag–AgBr nanospheres with the strong visible light response and effective separation of electron-hole pairs. The active group and photocatalytic mechanism for the rapid pollutant removal were systematically explored. This work will open the window of TiO2 NTA based photoelectrodes for the applications in solar energy conversion and dyeing waste water purification. Display omitted •Ag–AgBr nanospheres were prepared on TiO2 NTs by a simple hydrothermal method.•The TiO2 NTs/Ag–AgBr (0.025) photoelectrode exhibited high photoelectrochemical performances.•The PEC mechanism for the degradation of pollutants was proposed.