Peony seed phospholipids (PPLs), a kind of multifunctional plant-like phospholipids were extracted from peony seed meal. We investigated the functional properties of PPLs and compared their emulsification performance in corn oil-peony seed oil o/w emulsion systems with that of soy lecithin (DPLs). The PPLs were characterized with the higher content of phosphatidylcholine (PC) (416 ± 28 mg/g) and lyso-phosphatidylcholine (LPC) (43 ± 14 mg/g) fractions, and lower content of phosphatidylethanolamine (PE) (71 ± 13 mg/g). The polyunsaturated fatty acids showed higher content (83.25%), with the highest content of linoleic acid (46.05%) in PPLs. PPLs-emulsions showed smaller average particle size and higher loaded peony seed oil content at pH 5, temperature 50 °C, and about 60% corn oil content. PPLs-emulsions imparted better hydroxyl radical scavenging efficiency and reducing power than DPLs. Our results suggest that PPLs can be used as emulsifiers with improved antioxidant properties.