A novel oxidation way of electrically protected and enhanced activated carbon fibers (ACF) activating peroxodisulfate (PDS) was adopted in this work for the degradation of aqueous Carbamazepine, a sort of typical persistent medical pollutant. The removal rate by PDS system, ACF adsorption system, ACF activating PDS system, electrolysis system, protected ACF electrolysis system, and electrically protected and enhanced ACF activating PDS system was studied. The influences of PDS initial concentration, voltage, and initial pH value on the degradation of carbamazepine were also researched. Besides, characteristics detection of activated carbon fibers and radical quenching were conducted to reveal the oxidation mechanism in electrically protected and enhanced ACF activating PDS system. The results showed that the removal rate of carbamazepine in electrically protected and enhanced ACF activating PDS system was much higher than that in other processes. The excessive high initial PDS concentration could not promote the removal rate of carbamazepine. The removal rate of carbamazepine increased with the increase of voltage and the decrease of initial pH value. Activated carbon fibers could be protected from oxidation damaging with free electron implantation in cathode in electrically protected and enhanced ACF activating PDS process, which greatly prolonged its service life and significantly improved the utilization rate of PDS.