The alkaloid extract of the whole plant of Gelsemium elegans has afforded four new alkaloids: N-desmethoxyrankinidine [1], 11-hydroxrankinidine [3], 11-hydroxyhuman-humantenine [4] and humantenirine [6]. The structures of 5 was established through X-ray crystallographic analysis, and the structures of the other three new alkaloids were deduced by spectral analysis (1H, 13C, APT, 2D-COSY and 2D-HETCOR).