<p>The search for low-cost, high-capacity, and energy storage materials with fast reaction kinetics is essential for the practical implementation and scalability of advanced battery technologies. In this paper, we construct an innovative self-supported Li₃VO₄/N-doped C nanoribbon (SS LVO/NC NBs) with a core (LVO)-shell (NC) structure through a coaxial electrospinning method. The nanoribbons with an intricately interwoven layered structure can significantly enhance the mechanical integrity of the hybrid, making it suitable for using as a self-supporting electrode. Moreover, the nanoribbons present a unique core–shell structure with NC as the shell and LVO as the core. NC shell not only improves the conductivity, but also helps to reduce the volume expansion of LVO during the charge/discharge cycling, thus contributing to the cycling stability of the hybrid electrode. As expected, the SS LVO/NC NBs demonstrated impressive electrochemical performance, with an initial charge/discharge specific capacity of 621.0/950.7 mAh g⁻¹ at a current density of 0.2 A g⁻¹. Remarkably, even at a charge/discharge current density of 4.0 A g⁻¹, the SS LVO/NC NBs maintain a substantial discharge capacity of 395.4 mAh g⁻¹ over 2000 cycles, highlighting their potential for high-performance energy storage applications.</p>