Narcissus tazetta L. (Amaryllidaceae) grows widely in Egypt. It is also cultivated as an ornamental plant and for the production of volatile oil. From N. tazetta a number of alkaloids were isolated, which were of great interest because of their effective antitumour and antiviral activities, particularly against the choriomeningitis virus. From the wild plant the alkaloids lycorine, homolycorine, and tazettine were isolated. The more polar alkaloid fractions of this plant are now under study. From the fresh bulbs of N. tazetta, the alkaloid 1 was isolated. Its structure was identified as 9-0-demethylhomolycorine based on FAB-MS, EI-MS, 1H- and 13C-NMR spectra, positive FeCl3 test for phenolic OH-group, 2D 1H,1H, 2D 13C,1H, and 2D 13C,1H long-range spectra, NOE-effects observed between CH3-N and both 11-H and 11c-H and between CH3-O and 11-H, and preparation of the corresponding 9-0-acetyl derivative of 1 (2). In conclusion, this paper describes for the first time the isolation of 9-0-demethylhomolycorine from N. tazetta. This substance may be chemotaxonomically important considering the interest of the plant and the biological activity shown by its alkaloids.