Laozao highland barley bread is a novel type of coarse grain bread, which is very popular among people. By sensory evaluation, electronic nose combined with gas chromatography-ion mobility spectrometry, the differences in the quality and volatile flavor substances of two types of bread (Laozao highland barley bread and sweet bread) were analyzed. Sensory evaluation showed significant differences in aroma between the two types of bread. According to the specific volume results, the sweet bread had a larger specific volume. The results of electronic nose analysis revealed a substantial difference in overall flavor between the two types of bread, with the response value of the Laozao highland barley bread on the sensor being higher. GC-IMS results showed that a total of 41 compounds were identified in both breads, with alcohols and aldehydes being the main compounds. The addition of laozao and highland barley increased the ester and alcohol contents in the bread while decreasing the content of ketones (P<0.05). Six differential compounds (isoamylol-D, isoamylol-M, 2,6-dimethylpyridine, octanone, ethyl acetate-D, butylbenzene) were screened out by OPLS-DA and ROAV, indicating that these substances made an important contribution to distinguishing the highland barley bread from the normal sweet bread. Through the Spearman correlation analysis, it was found that isoamylol-D, 2,6-dimethylpyridine, butylbenzene, and ethyl acetate-D had a relatively strong positive correlation with the T and P sensors of the electronic nose. This study provided data support and reference for reasonable differentiation of different bread types and the development of new whole grain bread.