The photoelectrocatalytic (PEC) process has attracted much attention in the field of the eliminating organic pollutants in the wastewater with simultaneous hydrogen evolution in the past decade. Development of photoelectrode with high photoelectrocatalytic activity and stability is a key to degrade of various toxic pollutants via PEC technology. Here, a novel nanoflower-like metal–organic framework loaded on black titanium dioxide nanotubes (Ce MOFs/Black-TNTs) were fabricated by the hydrothermal method. Moreover, in order to improve the efficiency of photocatalytic process, cobalt-copper-manganese complex-doped black titanium dioxide nanotubes (CCM/Black-TNTs) photocathode is prepared and coupled with the Ce MOFs/Black-TNTs photoanode for hydrogen evolution at the cathode in an H-type photoreactor. The total organic carbon (TOC) removal rate of 2, 4-dichlorophenoxyacetic acid (2, 4-D) reached 98% and the yield of H2 reached 160 mmol in 120 min of reaction. The possible PEC degradation pathway of 2, 4-D at Ce MOFs/Black-TNTs photoanode was also speculated by UV–visible absorption spectroscopy and liquid chromatography combined with mass spectrometer (LC-MS). This work could open new insight into rationally designing TiO2-based photoelectrocatalysts for PEC system.