AbstractThis communication contains a description of the isolation of muscaridine from Amanita muscaria L. The constitution of muscaridin is established as erythro‐4,5‐dihydroxy‐n‐hexyltrimethylammoniumchloride. The synthesis, starting from 2,3‐dihydropyran, leads to racemic muscaridine. The resolution of racemic muscaridine succeeded with di‐p. toluyl‐L‐ tartaric acid and with di‐p. toluyl‐D‐tartaric acid. The synthetic product has the same RF‐value, a fully identical infrared spectrum and equal optical rotation as the natural base. The syntheses of threo‐4,5‐dihydroxy‐n‐hexyltrimethylammoniumchloride and of 5‐hydroxy‐n‐hexyltrimethyla