AbstractLi‐ion batteries as energy storage devices need to be periodically charged for sustainably powering electronic devices owing to their limited capacities. Here, the feasibility of utilizing Li‐ion batteries as both the energy storage and scavenging units is demonstrated. Flexible Li‐ion batteries fabricated from electrospun LiMn2O4 nanowires as cathode and carbon nanowires as anode enable a capacity retention of 90% coulombic efficiency after 50 cycles. Through the coupling between triboelectrification and electrostatic induction, the adjacent electrodes of two Li‐ion batteries can deliver an output peak voltage of about 200 V and an output peak current of about 25 µA under ambient wind‐induced vibrations of a hexafluoropropene–tetrafluoroethylene copolymer film between the two Li‐ion batteries. The self‐charging Li‐ion batteries have been demonstrated to charge themselves up to 3.5 V in about 3 min under wind‐induced mechanical excitations. The advantages of the self‐charging Li‐ion batteries can provide important applications for sustainably powering electronics and self‐powered sensor systems.