High-purity litchi γ-aminobutyric acid (GABA) was prepared via separation and refinement through sequential alcohol precipitation, resin column chromatography, and crystallization. Through a static adsorption experiment, the 732 cation exchange resin was screened from nine different types of resins, where its adsorption and desorption rates reached 81.56% and 88.26%, respectively. Evaluation of the static adsorption kinetics indicated that adsorption on the resin was primarily controlled by liquid-film diffusion, and was also influenced by the combined effects of multiple diffusion processes, such as intraparticle diffusion and adsorption-desorption on the internal surfaces of the particles. A dynamic elution experiment revealed that the highest raw material utilization rate was achieved at a sample loading of 8.25 mg/g. By taking the purification efficiency and cost into comprehensive consideration, the optimal elution conditions were determined as follows: sample concentration: 1.0 mg/mL, sample loading flow rate: 1.0 mL/min, sample pH value: 4, eluent concentration: 1.5 mol/L, elution flow rate: 1.0 mL/min. Under these optimized conditions, the purity and yield of the obtained litchi GABA were 77.40% and 92.05%, respectively. By crystallization from the purified sample solution, the purity increased to 95.35%, and the structure of the obtained crystal was identified as GABA through nuclear magnetic resonance analysis. In conclusion, the present study demonstrated that a combination of alcohol precipitation, ion exchange column chromatography, and crystallization processes enabled the recovery of GABA from litchi at a purity of >95%. The results of this study can serve as a valuable technical reference for the development and utilization of litchi GABA.