High-energy-density Li-S batteries (LSBs) are considered as a promising next-generation energy-storage system. However, the sluggish redox kinetics and severe polysulfide shuttle effect in elemental sulfur cathodes, along with uncontrollable dendrite propagation in lithium metal anodes, inevitably depress the electrochemical performance of LSBs and impede their practical implementation. Motivated by a unique hierarchical geometry, specific chemical affinity, and nitrogen-enriched collagen component of natural skin fibers (SFs), here we proposed an effective structural engineering strategy for crafting an SF-derived superhierarchical N-doped porous carbon framework in situ implanted with nickel/graphitic carbon nanocages as a dual-role host to simultaneously address the challenges faced on the sulfur cathode and lithium anode in LSBs. The experimental results and theoretical calculation disclose that the implanted Ni nanoparticles and highly graphitic sp2 carbon nanocages together with doped N heteroatoms not only provide a synergetic trapping-catalytic-conversion effect for regulating soluble polysulfides with promoted redox kinetics in the cathode at both room and elevated (55 °C) temperatures but also yield Ni-enhanced lithiophilic N-heteroatom active sites in the host framework to control Li deposition and suppress Li dendrite growth in anodes. Combining the cathodic and anodic improvements further achieves a superb rate and cycling performance in full LSB cells with stable Coulombic efficiency, showing great potential in developing reliable LSBs.