A unified methodological approach to the analysis of complex mixtures of volatile organic compounds in various media (air, water, soil), implemented with the use of universal methodological and instrumental bases, is substantiated. The main analytical method is the highly sensitive multivariate capillary gas chromatography in combination with other effective processes (gas extraction, sorption concentration, thermal desorption, cryogenic focusing etc.) applied in the operational line for sampling, sample preparation, pulsed sample introduction etc. Based on the metrological studies of the proposed basic technique for the analysis of multicomponent impurities (27 compounds in air samples) the techniques for measurement in air and water samples of mixed substances: gasoline, kerosene, white spirit and solvent oil were developed. The suggested principles of universality and unification of the operating series provide intensification and cheapening of their ecological control and monitoring.