The alkaloid extract of the whole plant of Gelsemiam elegans has afforded four new alkaloids: N-desmethoxyrankinidine 111, 1 1-hydroxyrankinidine 131, 1 l-hydroxyhumantenine 151, and 1 1-methoxyhumantenine [7l, as well as the known alkaloids rankinidine 121, humantenine [4] and humantenirine 161. The structure of 5 was established through X-ray crystallographic analysis, and the structures of the other three new alkaloids were deduced by spectral analysis ('H, 13C, AFT, 2D-COSY and 2D-HETCOR).