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Bud derivatives (BDs) represent a category of botanicals obtained by macerating the meristematic tissues (buds or young sprouts) of plants; widely used since ancient times in complementary medicine, they remain poorly investigated to date. In this study, a contribution is made toward the identification of the correct “a posteriori” attribution of the botanical species in commercial BDs, which is very important for ensuring the quality and safety of these natural products. Excitation–emission matrix (EEM) fluorescence spectroscopy proved to be a rapid, non-destructive and low-cost analytical instrument for providing a preliminary qualitative characterization of the BDs, allowing for the identification of specific spectral regions related to flavonol compounds and cinnamic and benzoic acids, in agreement with the targeted chromatographic analysis (HPLC-DAD), which completely defined a phytochemical profile for each BD considered. This information will be implemented in the first web application for the recognition of vegetable buds, named GEMMAPP, which was designed by the Authors and is proposed as a tool and future scientific data repository for providing information about the main, typical BDs of the France–Italy Alcotra territory.