Oral stimulation is an important component of the sensory profile of Baijiu, yet how specific organic acids modulate the temporal progression of ethanol-induced irritation remains unclear. In this study, the roles of organic acids were investigated by integrating time-intensity sensory analysis with quantitative profiling of 23 organic acids across 11 representative Baijiu samples. Multivariate analyses highlighted lactic, acetic, hexanoic, and octanoic acids as major contributors to differences in dynamic perceptual trajectories. Validation experiments in both model solutions and authentic Baijiu matrices showed that lactic and acetic acids significantly delayed the onset and buildup of oral irritation. Hexanoic acid was identified as a potential contributor to stronger sensory responses, although this effect was not statistically confirmed in the validation test. These findings show that specific organic acids can selectively modulate the temporal features of ethanol-induced irritation in Baijiu and provide a framework for linking chemical composition with dynamic sensory perception.