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<i>Acer triflorum</i> Komarov is an important ornamental tree, and its seasonal change in leaf color is the most striking feature. However, the quantifications of anthocyanin and the mechanisms of leaf color change in this species remain unknown. Here, the combined analysis of metabolome and transcriptome was performed on green, orange, and red leaves. In total, 27 anthocyanin metabolites were detected and cyanidin 3-O-arabinoside, pelargonidin 3-O-glucoside, and peonidin 3-O-gluside were significantly correlated with the color development. Several structural genes in the anthocyanin biosynthesis process, such as chalcone synthase (<i>CHS</i>), flavanone 3-hydroxylase (<i>F3H</i>), and dihydroflavonol 4-reductase (<i>DFR</i>), were highly expressed in red leaves compared to green leaves. Most regulators (<i>MYB</i>, <i>bHLH</i>, and other classes of transcription factors) were also upregulated in red and orange leaves. In addition, 14 <i>AtrMYBs</i> including <i>AtrMYB68</i>, <i>AtrMYB74</i>, and <i>AtrMYB35</i> showed strong interactions with the genes involved in anthocyanin biosynthesis, and, thus, could be further considered the hub regulators. The findings will facilitate genetic modification or selection for further improvement in ornamental qualities of <i>A. triflorum</i>.