A novel Ti₃O₅/TiP₂O₇@MPCNFs nanocomposite was facilely prepared by electrospinning, sol–gel ripening and H₃PO₄ pre-impregnation activation treatment. The Ti₃O₅/TiP₂O₇@MPCNFs as a binder-free anode showed a synergistic lithium storage effect due to its topographical surface morphology, hierarchical nanostructure and special heterogeneous composition.