Lithium-sulfur (Li-S) batteries hold the potential to revolutionize energy storage due to the high theoretical capacity and energy density. However, the commercialization process is seriously hindered by the rapid capacity decay and low utilization of sulfur, caused by the inevitable slow dynamics and the “shuttle effect”. The incorporation of metal-based electrocatalysts into sulfur cathodes shows promise in promoting the conversion of lithium polysulfides (LiPSs), reducing the “shuttle effect”, and enhancing cell kinetics and cycle life. Among these, Fe-based materials, characterized by environmental friendliness, low cost, abundant reserves, and high activity, are extensively used in sulfur cathode modification. This article reviews the advancements of Fe-based materials in enhancing Li-S batteries in recent years. Starting from single/multi-component Fe-based metal compounds and single/bimetallic atoms, the influence of different Fe coordination environments on the conversion mechanism of LiPSs is analyzed. It is hoped that this review and the proposed prospects can further stimulate the development and application of the Fe element in Li-S batteries in the future.