Headspace analysis has been successfully applied for determination of the solvent residues in vegetable oils and pharmaceuticals. Preconcentration and determination conditions for two groups of analytes (hexane, benzene, toluene, and chloroderivatives of hydrocarbons) were optimized. Limit of detection, linearity, repeatability and stability of standard mixture were estimated for all compounds. The method was applied to the analysis of real samples (vegetable oils, cardamol, vitamin A).