The electrically insulating and volumetric deformation of sulfur and the shuttle effect of the intermediate lithium polysulfide (LiPSs) have severely hindered the development of lithium-sulfur batteries (LSBs). Herein, a synergistic strategy of hierarchical porous nitrogen-doped carbon microspheres (PNCM) derived from low-cost biomass with surface-coated AlF3 nanolayer as a multifunctional sulfur host (denoted as PNCM@S@AlF3) was developed. The PNCM not only possesses an abundant pore structure, large surface area, and high electrical conductivity but also features an intrinsic N-doped and fluorinated framework, which effectively enhances the physical adsorption and chemical anchoring to LiPSs. In addition, the AlF3 nanolayer protects the open surface of the porous carbon to isolate sulfur species from the electrolyte to reduce irreversible losses while accelerating the redox kinetics of LiPSs through strong polar adsorption and bonding. Hence, the PNCM@S@AlF3 cathode exhibits an initial capacity as high as 1176.2 mAh/g at 0.2C, and the cycling stability and rate capability are superior to that of PNCM@S without AlF3 coating. Impressively, the PNCM@S@AlF3 cathode delivers stable long-term cycling performance at a high rate of 2C, with 95.6% capacity retention after 500 cycles. This work presents a facile, sustainable, and efficient synergistic strategy for developing advanced LSBs.