Ag3PO4/Ag4P2O7 nanospheres were deposited on the surface of TiO2 nanotube arrays/Ti mesh by the hydrothermal method, and the cetyltriethylammnonium bromide (CTAB) addition amount significantly influenced the morphology, phase composition, solar absorption, photoelectric conversion and photoelectrocatalytic (PEC) degradation of methylene blue (MB). The results indicated that the sample prepared with the CTAB addition of 0.025 g showed the optimal visible light photocurrent density (103.51 mu A/cm(2)), photovoltage ( - 0.19 V/cm(2)) and PEC efficiency (99.39%) for MB decomposition. The influence factors of PEC performances including external voltage and electrolyte concentration were further explored. Beside, the PEC mechanism of TiO2 NTs/Ag3PO4/Ag4P2O7 was tentatively proposed. The excellent photoelectrochemical activity of the three dimensional (3D) TiO2NTs/Ag3PO4/Ag4P2O7 photoelectrode would drive it prospective applications in solar cells and waste-water treatment.