Although ethanol dominates pungency perception in alcoholic beverages, variations among Baijiu samples with equivalent ethanol levels suggest additional modulators are involved. This study investigated the role of salivary physiology in modulating organic acid-induced temporal dynamics of pungency in Baijiu. Salivary α-amylase activity and total protein content were most closely associated with sensory dynamics. Higher amylase levels delayed onset and prolonged decline, whereas elevated protein corresponded to stronger and more persistent intensity. Acetic and hexanoic acids were identified as key modulators with distinct effects, while lactic acid functioned as a background factor with limited acute influence. Although mediation analysis didn't confirm statistical causality, validation demonstrated reproducible acid-specific impacts on salivary physiology. These results provide mechanistic insights into Baijiu pungency and highlight saliva as a critical physiological interface linking composition to sensory perception in complex food matrices.