Microfibrous-structured catalysts are materials that address the mass/heat transfer limitation and achieve catalytic process intensification, showing great promise for enabling practical environmental catalysis such as continuous wastewater treatment process. In this work, Fe3O4-doped ordered mesoporous carbon (OMC) catalyst supported on porous sintered metal fibers (Fe-OMC/SMFs) was prepared using a new yet simple "one-pot" method and used as a Fenton-like heterogeneous catalyst. The obtained catalysts were carefully characterized by TGA-DTG, BET, XRD, SEM-EDS, XPS and H-2-TPR techniques. Structured reactor was designed and developed using developed microfibrous-structured catalysts, demonstrating an excellent catalytic performance for continuous heterogeneous Fenton oxidation of phenol. Specifically, both phenol and H2O2 conversions increased slightly as carbonization temperatures increasing from 400 to 1000 degrees C. Compared to Fe-OMC pellet catalyst, the developed structured catalyst showed an improved catalytic activity (i.e. similar to 100 % phenol/H2O2 conversions), and remarkable long-term stability (i.e. similar to 100 % phenol conversion over a 7-h longevity test). Additionally, the developed Fe-OMC/SMFs catalyst showed Fe leaching amounts of similar to 10 mgL(-1) during reaction, being significantly lower than that of Fe-OMC pellet catalyst (i.e. similar to 500 mg L-1). Experimental results revealed that well-dispersed Fe3O4 nanoparticles in OMC and three-dimensional microfibrous networks and large void volume of SMFs support are significantly benefit to enhance mass transfer and contacting efficiency between active sites and reactants, and thus achieve the process intensification of catalytic degradation of phenol. (C) 2020 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.