The toxicity of the extracts of basidiocarp of Rhodophyllus rhodopolius was estimated by the effective dose inducing vomit in frogs. The ethanolic extract of the mushroom was submitted to dialysis, and the effective outer portion was chromatographed subsequently on cellulose, alumina, and reversed-phase ODS columns. The toxic vomiting principles that gave a positive Dragendorff reaction on a thin-layer chromatogram were isolated and identified with (2-hydroxyethyl) trimethylammonium salt (choline), tetrahydro-4-hydroxy-N,N,N,5-tetramethyl-2-furanmethanaminium salt (muscarine), and (4,5-dihydroxyhexy1)trimethylammonium salt (muscaridine), respectively, by comparison of lH NMR, 13C NMR, and mass spectral data with those of authentic samples.