AbstractThe shuttle effect and slow oxidation‐reduction reactions of the cathode in lithium‐sulfur batteries limit its practical application and development. Herein, porous carbon derived from pollen modified by black phosphorus nanosheets (BP/N−C) have been synthesized and utilized as a sulfur host in Li−S batteries. From the compositional outlook, the biomass‐derived carbon forms a unique three‐dimensional skeleton structure, exhibiting excellent properties, such as high porosity and high conductivity. Upon modified with black phosphorus, the BP/N−C composite materials demonstrate enhanced adsorption ability and catalytic activity toward lithium polysulfides (LiPSs). The BP/N−C/S cathode electrode presents a high initial specific discharge capacity of 1009.6 mAh g−1 and a low capacity decay rate of 0.08% per cycle during 150 cycles at 0.2 C rate. Besides, the BP/N C/S cathode electrode exhibits the superior rate performance (508 mAh g−1 at 5 C).