Na₃V₂(PO₄)₂F₃ is a typical NASICON structure with a high voltage plateau and capacity. Nevertheless, its applications are limited due to its low conductivity and poor rate performance. In this study, nitrogen–boron co-doped carbon-coated Na₃V₂(PO₄)₂F₃ (NVPF-CNB) was prepared by a simple sol–gel method using an ionic liquid (1-vinyl-3-methyl imidazole tetrafluoroborate) as a source of nitrogen and boron for the first time. The morphology and electrochemical properties of NVPF-CNB composites were investigated. The results show that a nitrogen–boron co-doped carbon layer could increase the electron and ion diffusion rate, reduce internal resistance, and help alleviate particle agglomeration. NVPF-CNB-30 exhibited better rate performance under 5C and 10C charge/discharge with initial reversible capacities of 99 and 90 mA h g⁻¹, respectively. Furthermore, NVPF-CNB-30 illustrates excellent cyclic performance with the capacity retention rate reaching 91.9% after 500 cycles at 5C, as well as a capacity retention rate of about 95.5% after 730 cycles at 10C. The evolution of the material's structure during charge/discharge processes studied by in situ X-ray diffraction confirms the stable structure of nitrogen–boron co-doped carbon-coated Na₃V₂(PO₄)₂F₃. Co-doping of nitrogen and boron also provides more active sites on the surface of Na₃V₂(PO₄)₂F₃, revealing a new strategy for the modification of sodium-ion batteries.