Ag3VO4 nanograss was deposited on the surface of vertically grown TiO2 nanotube arrays (TiO2 NTs) by a successive ion layer adsorption and reaction (SILAR) method, and the Ag3VO4 nanograss was further transformed into Bi11VO19 by the solvothermal ion exchange method. The formation of Bi11VO19 was influenced by solvothermal intervals, and the TiO2 NTs/Bi11VO19 exhibited outstanding visible light response and photoelectrochemical activity. The TiO2 NTs/Bi11VO19 (3) prepared with solvothermal treatment for 3 h showed the optimal photoelectric conversion and photoelectrocatalytic (PEC) properties. The transient photocurrent density, photovoltage and charge carrier concentration achieved 9.53 mA/cm2, −0.29 V and 1.36 × 1020 cm−3, respectively. Furthermore, the PEC rate constants of TiO2 NTs/Bi11VO19 (3) for the MO, RhB and MB degradation achieved 3.56 × 10−3, 9.01 × 10−3 and 2.30 × 10−2 min−1, respectively. The PEC removal efficiency of Cr(VI) was 86.62%. The outstanding photoelectric activity drives the TiO2 NTs/Bi11VO19 photoelectrode prospective applications in waste-water purification and solar cells.