The existence of micropollutants (MPs) including pathogens in waters poses great risks to ecological safety and human health. Sulfate radical (SO4•−)‒based advanced oxidation processes (AOPs) have attracted considerable attention in water treatment for both disinfection and removal of emerging MPs. Here, we investigated the SO4•−‒mediated kinetic and mechanistic aspects of simultaneous inactivation of Enterococcus faecalis (E. faecalis) and degradation of carbamazepine (CBZ), a typical MP with high occurrence in wastewater. In the absence of CBZ, (73.8 ± 2.3) % E. faecalis were inactivated after 12 min of treatment, while in the presence of CBZ, (68 ± 1.6) % of E. faecalis were inactivated, exhibiting similar inactivation efficiency with or without MP. The second‒order rate constant (k) of E. faecalis reacting with SO4•− was determined to be (5.42 ± 0.64) × 109 M−1 s−1. In addition, two distinct types of disinfection models, one based on the quenching ratio (Q model) and the other on steady‒state concentration of SO4•− (R model), were developed to predict the inactivation kinetics of E. faecalis. Both models exhibited good performance for describing the disinfection of E. faecalis with RMSE of 0.065 and 0.048, respectively. Our kinetic experimental and modelling results on bacterial disinfection and degradation of CBZ were projected to offer valuable insight into future developments for typical wastewater scenarios where microorganisms and MPs coexist.