Low anaerobic biological conversion rate is a challenge in the anaerobic biological treatment of phenol wastewater. The dominant syntrophic acetate oxidation and hydrogenotrophic methanogenesis (SAO-HM) pathway is expected to solve the problem. However, there are raw studies on artificially simulating a dominant SAO-HM pathway for enhancing the anaerobic bio-conversion of phenol. In this study, Fe3O4 and micro-hydrogen (Fe3O4/H2) was used to strengthen the anaerobic bio-conversion of phenol by simulating the dominant SAO-HM pathway. The results suggested Fe3O4 and H2 had a coupling promotion on the anaerobic bio-conversion of phenol and Fe3O4/H2 increased the relative abundance of Syntrophus (29.35%), Syntrophorhabdu (3.27%), Clostridium (3.01%) and Methanobacterium (65.74%), indicating Fe3O4/H2 formed a dominant SAO-HM pathway. However, Fe3O4/H2 obviously reduced the conductivity of sludge, the extracellular protein and the functional gens pilA, pilB and OmcS, implying direct interspecies electron transfer (DIET) generated by Fe3O4 was interfered by micro hydrogen in extracellular electron transport process which reduced the efficiency of extracellular electron transport. This study remind that extracellular electron transport cannot be ignored in the dominate SAO-HM pathway for the anaerobic bio-conversion of phenol.