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Sesquiterpenes are important defensive secondary metabolites and aroma components. However, limited information is available on the mechanism of sesquiterpene formation and composition in the non-heading Chinese cabbage (NHCC) leaf. Therefore, headspace solid-phase microextraction/gas chromatography-mass spectrometry (HS-SPME/GC-MS) combined with transcriptome analysis was used to study the mechanism of volatile organic compound formation. A total of 26 volatile organic compounds were identified in two NHCC cultivars 'SZQ' and 'XQC' and their F1 hybrids. Among these, sesquiterpene β-caryophyllene was identified only in 'XQC' and F1. Five genes encoding caryophyllene synthase were identified. The candidate β-caryophyllene synthase genes BcTPSa11 and BcTPSa21 had high expression levels only in 'XQC' and F1. In addition, several transcription factors of MYB-related, MYB, bHLH, and AP2/ERF families were identified by co-expression, suggesting that they regulate β-caryophyllene biosynthesis. Our results provide a molecular basis for sesquiterpene biosynthesis as well as insights into the regulatory network of β-caryophyllene in NHCC., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Authors.)