Hot-pressed flaxseed oil is favored in Northwest China as cooking oil due to its flavor and oxidative stability. The mechanism of enhancing oxidation stability of hot-pressed flaxseed oil by neoformed Maillard reaction products (MRPs) remains mysterious. Maillard model reaction between phosphatidylethanolamine (PE) and reducing sugar of flaxseed, glucose (Glu)/fructose (Fru)/xylose (Xyl), was conducted to investigate the antioxidant characteristics of products. MRPs of PE-Xyl had a superior reactivity and anti-oxidative capabilities, which could improve the oxidative stability of flaxseed oil and inhibited the formation of aldehydes in the accelerated oxidation. Phosphatidylethanolamine-linked pyrrolecarbaldehyde (PLP) was the main antioxidant component in MRPs of Xyl-PE by MS and NMR analysis and verification of antioxidant activity. Furthermore, the results of quantum chemical calculation show that the antioxidant activity center of PLP is the pyrrole group. The findings of this study provide insights into the chemical basis underlying the improved oxidative stability of hot-pressed oils.