In this paper, highly efficient activated carbon fiber (ACF) anode was prepared for the electro-catalytic oxidation of phenol. The ACF was firstly coated with TiO2 via ship-in-a-bottle synthesis, and then loaded with polyaniline (PANI) layer by an in situ polymerization. The TiO2 coating would improve electro-catalysis activity of ACF anode and the PANI coating would enhance its conductivity, transferring more electrons for electro-catalysis process. The cyclic voltammetry (CV) results of ACF, TiLO2/ACF, PANI/ACF and PANI/TiO2/ACF anodes implied that the dual coating could not only inhibit the generation of non-conductive polyphenol film on PANI/ACF anode (anti-passivation), but also obviously increase the phenol degradation efficiency of TiO2/ACF anode. The results of (OH)-O-center dot output and phenol removal rate showed that the working performance and stability of dual-coated ACF anode could be optimized through altering the modification amount of PANI and TiO2. The new mechanism of synergistic electrocatalysis of PANI/TiO2/ACF for phenol oxidative degradation was reported. The experimental results could offer a novel method to prepare highly efficient porous carbon anodic materials. (C) 2019 Elsevier Inc. All rights reserved.