Baijiu-peanut pairing is a popular food combination, wherein peanuts, particularly their lipid component, possess the potential to influence the flavor of baijiu and consequently modulate its aftertaste. To reveal the role of peanut lipid within this system, headspace experiments and equilibrium constant measurements were conducted. It was determined that peanut lipids are capable of inhibiting the release of flavor substances in baijiu, and this inhibitory effect is concentration-dependent. Molecular dynamics simulation results show a strong interaction between peanut lipids and ethanol (E binding = -2.181 kJ/mol), which weakens the binding energy between ethanol and compounds, resulting in 1 + 1 <
2 effect. The Intraoral SPME experiment revealed the retention effect lipid-coating on the aroma release of baijiu. The flavor substances retained in the oral coating can continuously contribute to the aftertaste perception of baijiu. Peanut lipids, leveraging the Marangoni effect of ethanol, play a role in prolonging the aftertaste of baijiu, either through direct or indirect ways. This study provides a scientific basis for understanding the complex flavor experience in the food pairing process.