<p>Element doping is one of the primary strategies to enhance the charge–discharge performance of LiFePO₄ cathode materials. In this study, Zn²⁺-doped LiFePO₄ was synthesized via an inorganic-based sol–gel method using ZnCl₂ as the zinc source. Structural evolution of LiFePO₄ before and after Zn²⁺ doping was characterized using techniques such as X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and Raman spectroscopy, confirming the successful substitution of Fe²⁺ by Zn²⁺ within the LiFePO₄ lattice. The electrochemical performance of the samples was investigated through cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge–discharge cycling tests, and rate capability tests. Results demonstrate that LiFe_0.95Zn_0.05PO₄ exhibits superior capacity and rate performance. At a 0.2C rate, the initial discharge specific capacity reaches 139.0 mAh/g, representing a 21.30% improvement over undoped LiFePO₄. Furthermore, the sample retains a 94.80% capacity retention rate after 100 cycles at 0.5C, with a Li⁺ diffusion coefficient of 4.25 × 10⁻¹⁴ cm²/s. These enhancements are primarily attributed to Zn²⁺ substitution, which strengthens Fe–O bonds, stabilizes the crystal structure, improves structural stability, and accelerates Li⁺ migration rates. Consequently, this doping strategy significantly enhances the discharge specific capacity, rate capability, and cycling performance of LiFePO₄.</p>