A simple micro-sampling system is described which facilitates isolation and concentration of complex organic constituents into three fractions of different volatilities. The method involves the headspace trapping of very volatile components from a complex matrix onto a porous polymer, Tenax GC, followed by the solvent elution of the matrix and the subsequent fractions of the eluate into volatile and less-volatile fractions. The headspace and the volatile fractions are then analyzed by high-resolution capillary gas chromatography. The less-volatile fraction is analyzed by high-performance liquid chromatography. Experimental details and the results obtained using tobacco leaves as a complex organic matrix are presented