In the current work, the ternary TiO2@C/FeTiO3 (TCF) hollow nanotubes are synthesized using MOF-Fe nanorods as a sacrificial template and precursor via the thermal carbonization under N-2 atmospheres. Due to such delicate structure features that consist of hollow needle-like framework, middle conductive-layer carbon and monodisperse FeTiO3 nanoparticles embedded on carbon layer, the hollow TCF composites can effectively harvest full spectrum light energy, enhance the interfacial charge separation and suppressed the recombination of photogenerated electron-hole pairs, resulting in enhanced photoelectrocatalytic (PEC) activity. Among as synthesized samples, TCF-20% photoanode exhibits the best performance towards the degradation of phenol under full spectrum light irradiation with an anodic bias of 1.5 V vs. SCE and the degradation rate constant is 0.586 h(-1), which is 2.75 times larger than that of the corresponding sum of both EC and PC process. In addition, triple synergistic effects of the possible mechanism with the enhancement of PEC activity was proposed on the basis of PEC degradation results. This work also opens a new insight for synthesis of photocatalysts based on novel MOFs.