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Developing high‐performance carbonaceous anode materials for sodium‐ion batteries (SIBs) is still a grand quest for a more sustainable future of energy storage. Introducing sulfur within a carbon framework is one of the most promising attempts toward the development of highly efficient anode materials. Herein, a microporous sulfur‐rich carbon anode obtained from a liquid sulfur‐containing oligomer is introduced. The sodium storage mechanism shifts from surface‐controlled to diffusion‐controlled at higher synthesis temperatures. The different storage mechanisms and electrode performances are found to be independent of the bare electrode material's interplanar spacing. Therefore, these differences are attributed to an increased microporosity and a thiophene‐rich chemical environment. The combination of these properties enables extending the plateau region to higher potential and achieving reversible overpotential sodium storage. Moreover, in‐operando small‐angle X‐ray scattering (SAXS) reveals reversible electron density variations within the pore structure, in good agreement with the pore‐filling sodium storage mechanism occurring in hard carbons (HCs). Eventually, the depicted framework will enable the design of high‐performance anode materials for sodium‐ion batteries with competitive energy density. [ABSTRACT FROM AUTHOR]