In this study, β-MnO2 was introduced into electro-peroxymonosulfate process as particle electrodes (E/PMS/β-MnO2) to reveal the pathway of reactive manganese species (RMnS) and its promoting effect on reactive oxygen species (ROS) production. A significant synergistic was observed in the E/PMS/β-MnO2 process, the reaction constant was 3 times higher than that in the E/PMS process. The mechanism experiments revealed the generation pathway of Mn(III)aq during the E/PMS/β-MnO2 process. The pyrophosphate complex experiments and electrochemical analysis demonstrated that Mn(III)aq was dominantly generated through the electron transfer between carbamazepine (CBZ) and Mn(IV) under electric field conditions, rather than the reduction process in the cathode area. Furthermore, quenching experiments and competition kinetics method demonstrated the production of Mn(III)aq has the potential to enhance the formation of reactive oxygen species (ROS), especially •OH and SO4•−. In addition, Mn(V)aq and Mn(VI)aq was proved unable to be produced during the E/PMS/β-MnO2 process. Different from other similar electrochemical studies, 1O2 was mainly generated by the reaction betweenO2•− and •OH in this research. It was observed that the inclusion of Cl— facilitated the removal of CBZ, whereas the addition of humic acid (HA) had negligible impact on CBZ removal during the E/PMS/β-MnO2 process. At last, the results of various water matrices effects and toxicology analysis showed that the E/PMS/β-MnO2 process has satisfactory performance in practical application. This study could provide new insights for electro-persulfate treatment processes.