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Bryophyllum daigremontianum is a very important traditional medicine and ornamental plant. Although Bryophyllum and Kalanchoe have been supported to form a clade, however, lack of chloroplast genomic severely hinders our understanding the phylogenetic relationships between them. In this study, the complete chloroplast genome of B. daigremontianum is first presented. It is 150,058 bp in length consisted a large single-copy (LSC, 82,164 bp) and a small single-copy (SSC, 17,042bp) separated by a pair of inverted repeats (IR, 25,426 bp) including 86 protein-coding genes, 37 tRNA, and 8 rRNA. Phylogenetic analysis supported that B. daigremontianum was closer to K. tomentosa than other species, which showed that chloroplast genome sequences offer a useful resource for future phylogenetic studies of Kalanchoe and Bryophyllum species.