AbstractLithium–sulfur batteries (LSB) with high theoretical energy density are plagued by the infamous shuttle effect of lithium polysulfide (LPS) and the sluggish sulfur reduction/evolution reaction. Extensive research is conducted on how to suppress shuttle effects, including physical structure confinement engineering, chemical adsorption strategy, and the design of sulfur redox catalysts. Recently, the rational design to mitigate shuttle effects and enhance reaction kinetics based on physical field effects has been widely studied, providing a more fundamental understanding of interactions with sulfur species. Herein, the physical field effect is focused and their methods and mechanisms of interaction are summarized systematically with LPS. Overall, the working principle of LSB system, the origin of the shuttle effect, and kinetic trouble in LSB are briefly described. Then, the mechanism and application of rational design of materials based on physical field effect concepts and the external physical field‐assisted LSB are elaborated, including electrostatic force, built‐in electric field, spin state regulation, strain engineering, external magnetic field, photoassisted and other physical field‐assisted strategies are pivotally elaborated and discussed. Finally, the potential directions of physical field effects in enhancing the performance and weakening the shuttle effect of high‐energy LSB are summarized and anticipated.