| Summary: | <i>Tetrastigma hemsleyanum</i> Diels et Gilg is a rare and wild medicinal resource. Metabolites, especially secondary metabolites, have an important influence on <i>T. hemsleyanum</i> adaptability and its medicinal quality. The metabolite proanthocyanidin (PA) is a polyphenol compound widely distributed in land plants, which can be used as antioxidants and anticancer agents. Here, we discovered that three types of PA accumulated in large amounts in purple leaves (PL), but not in green leaves (RG), based on widely non-targeted metabolomics. In addition, we further found that catechins and their derivatives, which are the structural units of PA, are also enriched in PL. Afterwards, we screened and obtained five key genes, <i>DNR1</i>/<i>2</i>, <i>ANS</i>, <i>ANR</i> and <i>LAR</i> closely related to PA biosynthesis through transcriptome analysis and found they were all highly expressed in PL compared to RG. Therefore, observed the regulatory relationship between the main compounds and genes network, and the PA metabolism regulatory pathway was complicated, which may be different to other species.
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