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New pesticides based on natural products are urgently needed, in consideration of their environmental care and lower collateral effects. Neem oil, the main product obtained from Azadiractha indica A. Juss, commonly known as neem tree, is mainly used in medical devices, cosmetics and soaps, as well as important insecticide. Manufacturing of neem oil first includes the collection of the neem seeds as raw material used for the extraction. Neem cake is the waste by-product remaining after extraction processes. The quality of the oil, as that of the cake, strictly depends from the quality of seeds as well as from the type of extraction processes used, which strongly influences the chemical composition of the product. Currently, the different types of commercial neem cake on the market are roughly identified as oiled and deoiled cake, but several other differences can be detected. The differences are relevant and must be determined, to obtain the necessary correlation between chemical constitution and larvicidal activities. Six different batches of neem cake, marketed by several Indian and European companies, were analyzed by HPLC and HPTLC, and their fingerprints compared, obtaining information about the different compositions, focusing in particular on nortriterpenes, considered as the main active components of neem oil. Therefore, the chemical composition of each cake was connected with the biological activitiy, i.e., the effects of the extracts of the six neem cakes were tested on eggs and larvae of Aedes albopictus (Stegomyia albopicta) (Diptera: Culicidae), commonly known as Asian tiger mosquito. The results confirmed the previously reported larvicide effects of neem cake that, however, can now be related to the chemical composition, in particular with nortriterpenes, allowing in that way to discriminate between the quality of the various marketed products, as potential domestic insecticides.