The objective of this study was to investigate the influence of Ala-Lys-Arg-Ala (AKRA), a tetrapeptide newly identified from Chinese Sesame flavor-type Baijiu in our previous work, on its binding ability with aroma compounds. A method using headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME-GC/MS) was employed to determine the corresponding binding ability between different concentrations of AKRA (10 - 1000 μg/L) and aromas in Baijiu. In comparison, the aroma molecules in Baijiu before and after adding AKRA were almost the same; only their volatility was altered, with mostly the esters, alcohols, and phenolic compounds being decreased. Additionally, AKRA slightly changed the whole aroma profile of Baijiu, especially with respect to p-cresol (an off-odor in sesame-flavor-type Baijiu), which was verified by systematic sensory experiments including gas chromatography-olfactometry (GC-O) and odor activity values (OAVs) analysis. The nonvolatile tetrapeptide favored the hydrogen bond interactions with p-cresol, forming the AKRA- p-cresol complex, thus reducing the headspace concentration of phenolic off-flavors as evidenced by HS-SPME-GC/MS, ultraviolet (UV) absorption spectroscopy, and nuclear magnetic resonance spectrum (1H NMR) analysis. Meanwhile, the hydrogen bond interaction was further confirmed with the intermolecular cross-peaks between the carboxyl hydrogen of AKRA and the phenolic hydroxyl of p-cresol by nuclear Overhauser effect spectroscopy (1H-1H NOESY).