•The aroma compounds in Hanyuan Zanthoxylum bungeanum were identified by GC × GC-O-MS.•72 volatile compounds were identified by GC-O-MS, of which 28 were aroma-active.•116 volatile compounds were identified by GC × GC-O-MS, 43 of which were aroma-active.•23 important aroma-active compounds with FD ≥ 27 were identified by AEDA.•Compounds were quantified by external standard curves and OAV. The present study sought to characterize the composition of volatile aroma compounds and key aroma-active compounds of dried Hanyuan Zanthoxylum bungeanum. The volatile aroma compounds were analyzed by the solid-phase microextraction (SPME) combined with gas chromatography–olfactometry-mass spectrometry (GC-O-MS) and two-dimensional comprehensive gas chromatography–olfactometry-mass spectrometry (GC × GC-O-MS). The key aroma-active compounds were analyzed by the aroma extract dilution analysis and odor activity value. A total of 72 volatile compounds were identified by GC-O-MS, of which 28 were aroma-active. Meanwhile, 116 volatile compounds were identified by GC × GC-O-MS, of which 43 were aroma-active. These results revealed that myrcene, (+)-limonene, (E)-β-ocimene, β-cubebene, Germacrene D, cineole, linalool, and linalyl acetate were the key aroma-active compounds of dried Hanyuan Zanthoxylum bungeanum.