Despite the significant progress in the fabrication of advanced electrode materials, complex control strategies and tedious processing are often involved for most targeted materials to tailor their compositions, morphologies, and chemistries. Inspired by the unique geometric structures of natural biomacromolecules together with their high affinities for metal species, we propose the use of skin collagen fibers for the template crafting of a novel multicore–shell Fe2N–carbon framework anode configuration, composed of hierarchical N-doped carbon nanofiber bundles firmly embedded with Fe2N nanoparticles (Fe2N@N-CFBs). In the resultant heterostructure, the Fe2N nanoparticles firmly confined inside the carbon shells are spatially isolated but electronically well connected by the long-range carbon nanofiber framework. This not only provides direct and continuous conductive pathways to facilitate electron/ion transport, but also helps cushion the volume expansion of the encapsulated Fe2N to preserve the electrode microstructure. Considering its unique structural characteristics, Fe2N@N-CFBs as an advanced anode material exhibits remarkable electrochemical performances for lithium- and potassium-ion batteries. Moreover, this bio-derived structural strategy can pave the way for novel low-cost and high-efficiency syntheses of metal-nitride/carbon nanofiber heterostructures for potential applications in energy-related fields and beyond.[Figure not available: see fulltext.].