Electrocatalytic performance of high-entropy ceramics have been recognized as a pivotal prerequisite to realizing ultra-durability for Li-S batteries. However, the dynamics of accurately capturing Li2S4 are full of unknowns, thus a comprehensive understanding of the mechanism between dynamic control factors and electrocatalytic performance remains largely unexplored. Here, we visually present the Li2S4 electrocatalytic process and accurately identify that high-entropy engineering of rare earth sites leads to positive modifications in crystal field splitting energy and electronegativity. In conjunction with theoretical analysis, the adsorption energy of Li2S4 is optimized by the electronic structure and covalency under dual-fields (electric field and crystal field) regulation, lead to efficient electrocatalytic performance. These findings have enabled us to develop a run of more than 10000 hours of ultra-durable ceramic electrocatalyst (La0.15Nd0.15Sm0.4Eu0.15Gd0.15)2Zr2O7 as sulfur cathode (HEZO-S). This basic understanding of the intrinsic relationship provides a feasible high-entropy strategy for the design of advanced catalysts for lithium-sulfur batteries.