The chief culprit impeding the commercialization of lithium–sulfur (Li–S) batteries is the parasitic shuttle effect and restricted redox kinetics of lithium polysulfides (LiPSs). To circumvent these key stumbling blocks, incorporating electrocatalysts with rational electronic structure modulation into sulfur cathode plays a decisive role in vitalizing the higher electrocatalytic activity to promote sulfur utilization efficiency. Breaking the stereotype of contemporary electrocatalyst design kept on pretreatment, field‐assisted electrocatalysts offer strategic advantages in dynamically controllable electrochemical reactions that might be thorny to regulate in conventional electrochemical processes. However, the highly interdisciplinary field‐assisted electrochemistry puzzles researchers for a fundamental understanding of the ambiguous correlations among electronic structure, surface adsorption properties, and catalytic performance. In this review, the mechanisms, functionality explorations, and advantages of field‐assisted electrocatalysts including electric, magnetic, light, thermal, and strain fields in Li–S batteries have been summarized. By demonstrating pioneering work for customized geometric configuration, energy band engineering, and optimal microenvironment arrangement in response to decreased activation energy and enriched reactant concentration for accelerated sulfur redox kinetics, cutting‐edge insights into the holistic periscope of charge‐spin‐orbital‐lattice interplay between LiPSs and electrocatalysts are scrutinized, which aspires to advance the comprehensive understanding of the complex electrochemistry of Li–S batteries. Finally, future perspectives are provided to inspire innovations capable of defeating existing restrictions.