<p>Hesperidin (HSPD) readily precipitates from concentrated orange juice (COJ) due to its low solubility, leading to a decline in both sensory and nutritional value of COJ. Based on the solubilizing effect of epigallocatechin gallate (EGCG) toward HSPD and its limitation of insufficient application stability in COJ, four polysaccharide-EGCG complexes were prepared via a self-assembly method to enhance the dissolution properties of HSPD and its solubility in COJ, using gum Arabic (GA), pullulan (P), sodium alginate (SA), and carboxymethyl cellulose (CMC), respectively. The polysaccharide-EGCG complexes were characterized through XRD, UV–Vis, FT-IR, and ζ-potential analysis, coupled with molecular docking simulation to investigate the solubilization pathway of HSPD by EGCG. The stability of polysaccharide-EGCG complexes under simulated environmental conditions and their HSPD-solubilizing efficacy were evaluated, and their application performance in COJ was assessed. The results indicated that the HSPD-solubilizing effect of EGCG was closely related to hydrogen bonding and π-π interactions, and this effect remained upon the incorporation of polysaccharides. Compared to EGCG alone, all four polysaccharide-EGCG complexes significantly improved the retention rate of EGCG and its HSPD-solubilizing efficacy under high-temperature and low-pH conditions. The retention rates were 83.17–99.00% and 83.63–98.15%, with the solubilization coefficients reached 2.46–4.17 and 2.38–4.07, respectively. Furthermore, the polysaccharide-EGCG complexes increased the solubility of HSPD in COJ by 8.21%-31.38% without negatively impacting the quality attributes of COJ, and the SA-EGCG complex showed superior efficacy. In conclusion, polysaccharide-EGCG complexes represent a green and promising strategy for enhancing HSPD solubility and improving the overall quality of COJ.</p>