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Abstract Lithium–sulfur (Li–S) batteries have been regarded as promising next‐generation energy‐storage devices owing to their inherently high theoretical energy density. Unfortunately, the poor capacity and cycling life caused by severe polysulfide shuttle effect and sluggish redox kinetics in sulfur cathodes greatly impede the practical application of Li–S batteries. Herein, a new class of nanonetwork‐structured carbon decorated with oxygen‐vacancy‐containing cerium oxide nanoparticles (NSC–CeO2−x), in which carbon skeleton is composed of highly conductive carbon nanotube core welded by hybrid carbon shell, has been developed via one‐step heating treatment of hybrid molecular brush and further employed as functional interlayer to modify separator of Li–S battery. Owing to the synergistic effect of the highly active CeO2−x nanoparticles and the three‐dimensional carbon nanonetwork in enhancing the preservation of the soluble polysulfides and boosting the redox kinetics of sulfur species, the NSC–CeO2−x significantly promotes the electrochemical performance of sulfur cathode. As a result, the as‐constructed Li–S batteries exhibit an ultrahigh initial sulfur utilization of 92.9% and an extremely large capacity of 751 mA h g−1 at a high rate of 5 C. Remarkably, a stable capacity of 728 mA h g−1 over 300 cycles at 1 C is also achieved.