The analysis of ~, 13, y, 8-tocopheroJs, trienoJs, ~-tocopheryJ acetate and nicotinate (vitamin E) in complex matrices was carried out using a new liquid chromatographic (HPLC) method giving better separation efficiency, selectivity and sensitivity than that described in the literature. The use of normal-phase (NP)-HPLC on silica gel with isooctane-diisopropylether-l,4-dioxane as optimized mobile phase yielded higher resolution than conventional reversed-phase (RP)-HPLC using methanol mobile phase. Identification of peaks was by UV-absorbance at 295 nm, diode array, or fluorescence detection ()~ex = 295 nm, )~ex = 330 nm). The latterwas found to be more selective and ten times more sensitive than UV-absorbance detection. A quadrupole, ion-trap mass spectrometerwith an atmospheric-pressure ionization (APCI) interface was used to detect vitamin E constituents in the femtomole range. With collision-induced dissociation (CID) in the ion source, which gave characteristic fragmentation, the identity of the investigated compounds could be confirmed. Plots of peak area versus amount injected allowed quantitation of ~, 13, y, 8-tocopherols and -trienols, ~-tocopheryl acetate and nicotinate in real samples such as peanut, almond, spinach, spelt grain bran, latex and tablets. The method described offers fast identification and quantitation of vitamin E constituents of complex biological origin.