To determine the types of volatile compounds in major peach balsamic vinegar brands in Hebei and distinguish the differences in their compound compositions, an electronic nose and gas chromatography-ion mobility spectrometry (GC-IMS) were used to analyze the characteristic flavor components of different brands of peach balsamic vinegar. The differences in aroma were also evaluated using multivariate statistical analysis. The results showed that the sensors responded more strongly to the sulfide and aromatic compounds of the volatile components of peach balsamic vinegar in the order of brand B>brand C>brand A. GC-IMS identified 79 volatile compounds, including 25 esters, 12 aldehydes, nine alcohols, eight ketones, six ethers, six pyrazines, three acids, three furans, and seven compounds of other types. The GC-IMS fingerprint also revealed 35 marker compounds shared by the three types of peach balsamic vinegar, with ethyl acetate and 2,6-dimethyl-5-heptenal (melonal) contributing to the fruity sweetness, and 2,6-dimethoxyphenol (syringol) contributing to the medicinal aroma of the vinegars. Principal component analysis validated effective discrimination between products using GC-IMS spectral data. Using an orthogonal partial least squares discriminant analysis model, 25 differential volatile compounds were identified by screening variables with a variable importance in projection value>1, followed by combined analysis with an S-plot. Total acids and sugars did not significantly differ among the products, and the overall acceptability in sensory evaluation was high for all three brands. The results of the present study demonstrated the utility of the electronic nose and GC-IMS in discriminating peach balsamic vinegars, providing a reference for quality assessment.