Abstract A controlled bioleaching strategy to embed Ni3S2 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 Ni3S2/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 Na3V2(PO4)3 as cathode (i.e., 218.9 mAh g−1 after 100 cycles at 0.5 A g−1).