One hundred and six ornamental varieties of Narcissus were analysed by GC-MS in an attempt to determine their alkaloid profile and the relationships between them were explored by multivariate statistical methods. Leaf and bulb tissues were analysed separately. A total of 61 Amaryllidaceae alkaloids and 2 protoalkaloids were identified and quantified. Different alkaloid profiles were found in leaves and bulbs, with leaves showing a higher quantity and more complex profile of alkaloids. Important differences were also found among plant varieties, k-Means cluster analysis determined five clusters based on similarities in alkaloid composition in both leaves and bulbs. The predominant alkaloids were lycorine-type in leaves, and galanthamine-type in bulbs. A correspondence analysis suggested that a global relationship between horticultural divisions of ornamental Narcissus varieties and k-means clusters based on alkaloid composition was unlikely, although some clusters were found to be particularly associated with certain divisions.