Aliphatic and triterpene alcohols present in vegetable oils have been identified and determined by HPLC using UV-vis and MS detection after previous derivatization with diphenic anhydride. The alcoholic fraction was obtained by saponification, extraction and TLC (according to the European Union official procedure). Derivatization was performed in tetrahydrofuran in the presence of suspended grinded urea, which increases the reaction rate and yield. Derivatized extracts were chromatographed on a C8 column using gradient elution with acetonitrile/water mixtures containing 0.1% acetic acid, with UV-vis followed by negative-ion mode MS detection. Using linear discriminant analysis of the HPLC-MS data (extracted ion chromatograms), oil samples belonging to seven botanical origins (hazelnut, sunflower, corn, extra virgin olive, soybean, peanut and grapeseed) were correctly classified with excellent resolution among all the categories.