Abstract Lithium–sulfur (Li–S) batteries have attracted considerable attention over the last two decades because of a high energy density and low cost. However, the wide application of Li–S batteries has been severely impeded due to the poor electrical conductivity of S, shuttling effect of soluble lithium polysulfides (LiPSs), and sluggish redox kinetics of S species, especially under high S loading. To address all these issues, a Ni–CeO2 heterostructure‐doped carbon nanofiber (Ni‐CeO2‐CNF) is developed as an S host that combines the strong adsorption with the high catalytic activity and the good electrical conductivity, where the LiPSs anchored on the heterostructure surface can directly gain electrons from the current collector and realize a fast conversion between S8 and Li2S. Therefore, Li–S batteries with S@Ni‐CeO2‐CNF cathodes exhibit superior long‐term cycling stability, with a capacity decay of 0.046% per cycle over 1000 cycles, even at 2 C. Noteworthy, under a sulfur loading up to 6 mg cm−2, a high reversible areal capacity of 5.3 mAh cm−2 can be achieved after 50 cycles at 0.1 C. The heterostructure‐modified S cathode effectively reconciles the thermodynamic and kinetic characteristics of LiPSs for adsorption and conversion, furthering the development of high‐performance Li–S batteries.