There is an increasingly significant issue on decomposition of contaminants in modem chemical industry and environmental protection. Hence, in the study, to improve the catalytic of semiconductor materials, the silver silver bromide nanoparticles decorated reduced TiO2 nano-tube arrays photoelectrode (Ag-AgBr/r-TiO2 NTAs), which exhibits better photocatalytic (PC) performance in the wide range of solar spectra, was successfully fabricated by anodization process, followed by microwave reduction strategy. The partly reduced AgBr nano particles are decorated and both Ti3+ and states are simultaneously introduced in the TiO2 NTAs photo electrode inducing the formation of impurity energy level to form Ag-AgBr/r-TiO2 NTAs photoelectrode. Moreover, PC activity of Ag-AgBr/r-TiO2 NTAs photoelelctrode was measured by degradation of 4-chlorphenol (4-CP). Results suggest that Ag-AgBr/r-TiO2 NTAs photoelectrode exhibits higher PC activity (99.9%) than that of other samples within 120 min illumination. The well combination of surface plasmons Ag-AgBr nanoparticles and r-TiO2 NTAs was responsible for the enhancing of PC, and the recombination of photo-generated electrons and holes can simultaneously be inhibited. Thus, Ag-AgBr nanoparticles and Ti3+ exert huge influence on the PC and photoelectrochemical properties of Ag-AgBr/r-TiO2 NTAs photoelectrode.