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The shuttling behavior and slow conversion kinetics of the intermediate lithium polysulfides are the severe obstacles for the application of lithium‐sulfur (Li‐S) batteries over a wide temperature range. Here, an engineered lamellar yolk–shell structure of In2O3@void@carbon for the Li‐S battery cathode is developed for the first time to construct a powerful barrier that effectively inhibits the shuttling of polysulfides. On the basis of the unique nanochannel‐containing morphology, the continuous kinetic transformation of sulfur and polysulfides is confined in a stable framework, which is demonstrated by using X‐ray nanotomography. The constructed Li‐S battery exhibits a high cycling capability over 1000 cycles at 1.0 C with a capacity decay rate as low as 0.038% per cycle, good rate performance, and temperature tolerance at −10, 25, and 50 °C. A nondestructive in situ monitoring method of the interfacial reaction resistance in different cycling stages is proposed, which provides a new analysis perspective for the development of emerging electrochemical energy‐storage systems. [ABSTRACT FROM AUTHOR]