An unidentified snake specimen was collected from a heap of sticks and dry leaves in Xiangyindu Town, Yongxing County, Hunan Province, China (113°01′18″ E，26°11′87″ N, 174 m) during a biodiversity survey in early August 2022. Morphological characteristics comparison revealed that the collected specimen was generally consistent with the morphological characteristics of the Calamariaarcana from Guangdong Province, China. Bayesian and maximum likelihood phylogenetic analyses based on the mitochondrial gene fragment Cyt b showed a high support monophyletic group between the collected specimen with the C. arcana (PP 1.00, BS 100), and the uncorrected pairwise sequence divergence was 1%. Thus, based on morphological analysis and phylogenetic comparison, this specimen was finally identified as C. arcana, which is a new snake record in Hunan Province.