To investigate the aroma differences among different varieties of Chaotian pepper in Zunyi, volatile aroma components of 23 Chaotian pepper varieties from Zunyi were quantitatively analyzed using headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS). Their flavor characteristics were systematically analyzed combined with odor activity value (OAV), principal component analysis (PCA) and orthogonal partial least squares-discriminant analysis (OPLS-DA). The results showed that a total of 45 aroma components were identified, belonging to 9 categories, with total contents ranging from 400 mg·m?³ to 700 mg·m?³, among which aldehydes were the dominant components (accounting for 40.51 wt.%–72.23 wt.% of the total). OAV analysis screened out 28 key aroma-active components, including 17 common aroma components and 11 non-common components. The aroma profile radar chart showed that all varieties were dominated by floral aroma, with obvious differentiation in secondary aromas. A total of 12 key differential aroma components (VIP>1, P<0.05) were identified by OPLS-DA combined with variable importance in projection (VIP) and t-test, including 3 aldehydes, 2 hydrocarbons, 2 esters, and 1 each of acids, alcohols, ketones, furans and phenols. This study helps to clarify the aroma characteristics of different Chaotian pepper varieties, and provides a theoretical basis and technical support for flavor-oriented precise breeding and the development of high value-added products.