3D Lithiophilic Freestanding Hosts with SiOx‐Embedded Hierarchical Porous N‐Doped Carbon Nanofibers for Dendrite‐Free Lithium Metal Batteries

3D host materials are promising for Li-metal anodes (LMAs) because of their adaptability to volume changes and large areas that prevent current localization, hindering dendritic Li formation. Herein, freestanding porous N-doped carbon nanofibers (PCNFs) with uniformly distributed SiO_x are synthesized by electrospinning and subsequent carbonization. In these composites, tunnel-like, open channels are formed between the CNFs by removing polystyrene (PS) and the hollow N-doped nanocages (HNC) generated from zeolitic imidazolate frameworks-8 (ZIF-8) during carbonization, providing sufficient space for Li deposition. Accompanying these structural advantages, the adequate electron conductivity and lithophilic properties derived from the conductive N-doped CNFs and insulating SiO_x confer optimized characteristics for uniform Li distribution. The coulombic efficiency exceeds 98% over 160 cycles in asymmetrical cells at a current density of 2.0 mA cm^-2, with stable voltage hysteresis and an average overpotential of 25 mV for 1350 h in symmetrical tests. Full cells assembled with composite anodes predeposited with Li exhibited excellent capacity retention, delivering 141 mAh g^-1 at 2.0 C with LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) cathodes. The results highlight that the optimized combination of conductive CNFs, HNCs, and insulating SiO_x effectively enables uniform Li deposition, significantly enhancing cycling stability and Coulombic efficiency (CE) of LMAs.