Abstract: The non-biodegradable organic pollutants in the water environment pose a potential threat to human body and ecological environment. Thus, it is very important to develop efficient, environmental and low-cost catalytic systems to remove these contaminants. Biochar-based materials and PMS (peroxymonosulfate) systems, as advanced oxidation technologies, have potential applications in wastewater treatment. In order to clarify the properties and interfacial mechanisms of biochar and PMS to degrade organic pollutants, the catalytic activities and mechanisms of three typical biochar-based materials, including biochar, non-metal doped biochar and metal oxide-biochar are reviewed. The results show that the surface catalytic sites on biochar-based materials (such as oxygen-containing groups, defects, PFRs (persistent free radicals) and metal atoms) can oxidize PMS through radical or non-radical pathways. In this progress, the SO₄^-· (sulfate radical), ·OH (hydroxyl radical) and O₂^-· (superoxide radical) radicals are produced to promote the catalytic activity of the corresponding systems. Besides, non-metal doped biochar and metal oxide-biochar also have higher catalytic activities than pristine biochar due to the significantly difference in electric charge distributions and active sites. However, there are still some deficiencies in the present studies. For example, the synergistic mechanisms of various active sites in the activation of PMS by biochar-based materials are still unclear, the catalytic activity and mechanism of heteroatomic co-doped biochar or biochar-supported monatomic catalyst in the PMS systems need to be further studied, the synergistic mechanism of free radicals and non-free radical activation is unclear, and the influence of pollutant structure on the catalytic activity of biochar-based materials needs to be further explored.