Vincetoxicum hainanense is an endangered liana species endemic to China. Habitat destruction coupled with difficulties in natural pollination has reduced its population size over time. As present studies have focussed more on breeding programmes instead of molecular aspects, here we reported on the complete chloroplast (cp) genome sequence of V. hainanense. The cp genome is 161,280 bp in size and includes two inverted repeat (IR) regions of 24,884 bp each, which is separated by a large-single copy (LSC) region of 92,084 bp and a small-single copy (SSC) region of 19,428 bp. A total of 131 genes were predicted, including 37 tRNA, 8 rRNA, and 86 protein-coding genes. Phylogenetic analysis showed that V. hainanense is clustered with other Apocynaceae species and sister to Biondia chinensis.