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RG-I pectin has excellent health benefits, but its raw materials are relatively scarce, and its complex structure often breaks down its side-chain structure during the extraction process. In this study, the physicochemical and antioxidant properties of a branched-chain-rich pectin gained from watermelon peel were demonstrated, and the structure–function relationships of RG-I-enriched pectin and emulsification properties were investigated. Fourier transform infrared spectroscopy, high-performance anion exchange chromatography, high-performance gel permeation chromatography, nuclear magnetic resonance spectroscopy, and methylation analyses reveal it as acetylated, low-methoxylated pectin, rich in RG-I side chains (MW: 1991 kDa, RG-I = 66.17%, methylation degree: 41.45%, (Ara + Gal)/Rha: 20.59%). RPWP outperforms commercial citrus pectin in emulsification and stability, significantly preventing lipid oxidation in emulsions. It also exhibits free radical scavenging abilities, contributing to its effectiveness in preventing lipid oxidation. Emulsions made with RPWP show higher viscosity and form a weak gel network (G′ > G″), enhancing stability by preventing phase separation. These findings position watermelon peel as a good source of RG-I pectin and deepen our understanding of RPWP behavior in emulsion systems, which may be useful in the food and pharmaceutical fields. [ABSTRACT FROM AUTHOR]