How to exert the value-added superiority was a key link in the development of biomass valorization that heightens an appeal for a waste-minimized protocol. The fractional use of three building blocks in biomass became an urgent challenge to be faced. Herein, we report an autohydrolysis-aided biorefinery for the sequential conversion of wheat straw hemicelluloses, cellulose and lignin into xylooligosaccharides (XOS), fermentable glucose and lithium-sulfur cathode at the end of the process, respectively. The yield of XOS (DP of 2–6) reached up to 24.06% (w/w) of xylan and 6.19% (w/w) of the initial biomass. The hydrothermal treatment removed the amorphous portion and disrupted the rigid structure, thereby improving the cellulose digestibility from 14.1 to 88.9%. The molecular weights, functional groups and structural features of residual lignin after enzymatic hydrolysis were thoroughly explored for the cathode of lithium-sulfur batteries via the carbonizing process. Because of the considerable surface area, the covalent linkage between the lignin-derived carbon (LC) and sulfur, and the uniform dispersion of sulfur particles, the developed LC@S cathode exhibited excellent rate capability, and the specific capacity of 1238, 1085 and 1035 mA h g−1 at 0.1, 0.2 and 0.5 C, respectively. The LC@S cathode retained 596 mA h g−1 after 200 cycles at 0.5 C with a coulombic efficiency of 92%. The present study provides a systematic strategy that bears the primary responsibility for exploiting biomass into a potential feedstock with worthwhile functions in the thriving domains of chemicals, biofuels and energy storage devices.