In this study, a simple ceramic membrane aeration was used to realize dielectric barrier discharge/peroxymonosulfate (DBD/PMS) in-situ microbubble aeration for effective dispersion and gas–liquid transfer of highly active substances. Compared with conventional aeration, ceramic membrane aeration had 18 times fewer microbubble diameters (110–180 µm), much higher bubble densities, and 1.6–2.1 times higher aquatic O3 concentrations at pH 4.8–10.0. Consequently, the yield of HO and SO4·- was 1.64–2.34 and 1.13–2.93 times, respectively, via faster O3 transfer to the aquatic solution and enhanced PMS activation. DBD/PMS microbubble aeration outperformed conventional aeration, with a 2.52-fold increase in LEV degradation kinetics and a 2.79-fold increase in TOC removal. Quenching and EPR experiments showed that HO and 1O2 were the main reactive oxygen species (ROS) for LEV degradation. The yield of O2·- was higher at pH 6.9, while HO, SO4·-, and 1O2 was higher at pH 8.7 derived from a series of complex reactions. The LEV degradation pathway was pH-dependent, with the HO-oxidation contribution varying from 25.3% to 44.3% as the pH increased from 4.8 to 8.7, while other ROS (1O2 and O2·-)-oxidation decreased from 73.1% to 51.8%. Therefore, this work will advance the current understanding of the intrinsic effects of pH in the plasma/PMS microbubble process for wastewater purification.