The processes of lipids oxidation represent a great concern for the consumer health because they are one of the major causes of quality deterioration in fat-containing products. One of the most effective methods of delaying lipid oxidation consists in incorporating antioxidants. The present investigation describes the formulation of chitosan and novel glycol chitosan nanoparticles (NPs) loaded with alpha-Tocopherol (alpha Toc-NPs). The obtained NPs were characterized by various techniques, such as particle size (showing mean diameters in the range 335-503 nm) and zeta potential measurements, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The NPs were, then, added in the preparation of oil-in-water simple emulsion both to make the lipophilic alpha Toc available in an aqueous medium and to prevent emulsion oxidation. For this purpose, a new highly sensitive, simple and solvent-free method based on a solid phase microextraction (SPME) coupled to gas chromatography mass spectrometry was developed for the determination of alpha Toc in aqueous medium. All the parameters influencing SPME, including fiber coating, time and temperature extraction, pH, ionic strength and desorption conditions, have been carefully screened. The method was successfully applied to the determination of vitamin in the alpha Toc-NPs and its release from NPs-enriched simple emulsion formulations. SPME provided high recovery yields and the limits of detection and of quantification in emulsion were 0.1 and 0.5 mu g/mg, respectively. The precision of the method has been also estimated. The delay of the lipid oxidation by the proposed formulations has been evaluated exploiting the Kreis test on alpha Toc-NPs-enriched emulsions.