The aroma characteristics of Zanthoxylum schinifolium from four different production areas in Sichuan were identified and compared. Aroma components were analyzed via sensory evaluation, gas chromatography–olfactometry–mass spectrometry (GC–O–MS), and comprehensive two-dimensional gas chromatography-olfactometry-mass spectrometry (GC × GC–O–MS). The results revealed that minty, spicy, woody, fresh, citrus, and herbal notes could be perceived, with the Jinyang sample exhibiting the most significant aroma profile. Compared with GC–O–MS, GC × GC–O–MS offers advantages in identifying aroma-active compounds, and it can identify more types and quantities of aroma-active compounds. In this study, 40 aroma-active compounds from seven different classes were identified via GC × GC–O–MS. Through aroma extraction dilution analysis (AEDA), 14 aroma-active compounds were quantitatively analyzed, and odor activity values (OAVs) were calculated. Additionally, orthogonal partial least squares discriminant analysis (OPLS-DA) was employed to identify four aroma-active compounds with variable importance in projection (VIP) scores greater than 1, indicating their potential as identification markers. This study enhances our understanding of the sensory characteristics and aroma-active compounds of Zanthoxylum schinifolium.