Achieving high loading of active sulfur yet rational regulating the shuttle effect of lithium polysulfide (LiPS) is of great significance in pursuit of high-performance lithium-sulfur (Li-S) battery. Herein, we develop a free-standing graphene-nitrogen (N), phosphorus (P) and fluorine (F) co-doped mesoporous carbon-sulfur (G-NPFMC-S) film, which was used as a binder-free cathode in Li-S battery. The developed mesoporous carbon (MC) achieved a high specific surface area of 921 m²·g^–1 with a uniform pore size distribution of 15 nm. The inserted graphene network inside G-NPFMC-S cathode can effectively improve its electrical conductivity and simultaneously restrict the shuttle of LiPS. A high sulfur loading of 86% was achieved due to the excellent porous structures of graphene-NPFMC (G-NPFMC) composite. When implemented as a freestanding cathode in Li-S battery, this G-NPFMC-S achieved a high specific capacity (1,356 mAh·g^–1), favorable rate capability, and long-term cycling stability up to 500 cycles with a minimum capacity fading rate of 0.025% per cycle, outperforming the corresponding performances of NPFMC-sulfur (NPFMC-S) and MC-sulfur (MC-S). These promising results can be ascribed to the featured structures that formed inside G-NPFMC-S film, as that highly porous NPFMC can provide sufficient storage space for the loading of sulfur, while, the N, P, F-doped carbonic interface and the inserted graphene network help hinder the shuttle of LiPS via chemical adsorption and physical barrier effect. This proposed unique structure can provide a bright prospect in that high mass loading of active sulfur and restriction the shuttle of LiPS can be simultaneously achieved for Li-S battery.