Persulfate-based advanced oxidation processes (PS-AOPs) are considered as efficient techniques for the degradation of contaminants, whereas the effective activation methods for reactive oxygen species (ROS) generation play vital roles in PS-AOPs. However, the internal electric field mediated activation methods, like introducing chemicals and materials, are often restricted by their intrinsic properties. Conversely, the introduction of external fields can provide extra energy to remarkably enhance the PS activation performance from outside, acting as an additional impetus to promote the cleavage of OO bond and thus improve the generation efficiency of ROS. In this review, a comprehensive overview of the external field enhanced PS-AOPs from fundamentals to applications was introduced. Specifically, the activation mechanisms under different external fields, recent advances and their influencing factors, as well as potential practical applications of the external field enhanced PS-AOPs were summarized. The perspectives from the opportunity to challenge were thus made for future investigation. Therefore, this review is expected to give a systematic overview of external-field enhanced PS-AOPs, providing a new direction towards the improvement on catalytic efficiency of PS-AOPs through the rational utilization of external fields.