The development of natural and biodegradable polymer nanoparticles as Pickering emulsion stabilizers has attracted increasing interest. In this study, antioxidative pectin from hawthorn wine pomace (HP) was first produced. HP and zein-nanoparticles (ZPs) were used to fabricate zein-HP composite nanoparticles (ZHPs) via hydrogen bonding and electrostatic interaction. The ZHP composite at the HP-ZP ratio of 1:1 (w/w) exhibited near-neutral wettability (92.9o ± 1.01), thereby being used for stabilizing Pickering emulsion (ZHPEs). CLSM and cryo-SEM showed the anchoring of ZHPs onto the surface of oil droplets and the gel-like network structure in the continuous-phase. ZHPEs at 0.5–0.7 (v/v) oil fractions were pseudoplastic fluids with elastic-solid characteristics. ZHPEs with 0.6 and 0.7 (v/v) oil fractions showed excellent thermal stability 20–60 °C. The antioxidant capacity of HP helped protect the Pickering emulsion against its lipid oxidation. Therefore, antioxidative polysaccharides could stabilize Pickering emulsions as particle shell-materials while offering protection on lipid components against oxidation. This study has demonstrated the sustainable utilization of food waste for producing value-added products.