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A controlled bioleaching strategy to embed Ni 3 S 2 nanocrystals into 1D hollow carbonaceous fibers derived from renewable biomass was designed with enough inner voids as well as abundant natural pyridinic and pyrrolic nitrogen. The hollow fiber-based electrode can prevent the large volume expansion, improve the electronic conductivity and enhance the diffusion rate of Li+/Na+ ion. As a result, the synthesized Ni 3 S 2 /hollow carbonaceous fiber electrodes deliver excellent reversible capacity and outstanding cycle stability, i.e., 673.4 mAh g−1 at 0.1 A g−1 after 100 cycles for lithium-ion batteries (LIBs), 378.4 mAh g−1 at 1 A g−1 after 100 cycles for sodium-ion batteries (SIBs), in electrochemical half-cells. More importantly, a superior electrochemical performance is obtained in a full-cell when employing Na 3 V 2 (PO 4) 3 as cathode (i.e., 218.9 mAh g−1 after 100 cycles at 0.5 A g−1). Image 1 • A novel controlled bioleaching template-free approach to synthesize tunable hollow Ni 3 S 2 carbonaceous fibers. • 1D hollow carbonaceous fibers provide enough inner voids, abundant natural pyridinic and pyrrolic nitrogen. • The composites exhibit excellent lithium/sodium-ion storage performance for Half/Full Cell Applications. [ABSTRACT FROM AUTHOR]