Gas chromatography-ion mobility spectrometry (GC-IMS), gas chromatography-flame ionization detector (GC-FID), gas chromatography-mass spectrometry (GC-MS) and sensory evaluation were used to study the chemical flavor and sensory characteristics of sauce-flavor baijiu from four different origins in China. Totally 152 volatile compounds were identified, including esters, alcohols, ketones, and aldehydes. Through partial least squares discriminant analysis, 17 differential markers with variable importance in projection (VIP) value greater than 1 were selected from the 39 main volatile compounds to distinguish sauce-flavor baijiu from different origins. Sensory evaluation showed differences in the flavor characteristics of baijiu samples from the four origins which could be effectively identified by sensory evaluation and gas chromatography (GC). This study also clarified the material basis of the flavor difference, whose results provide a theoretical basis for the design of sauce-flavor baijiu body.