Mass spectrometry is often insufficient to distinguish between structural isomers, requiring confirmation using NMR spectroscopy. Here, a novel preparative technique based upon capillary multidimensional gas chromatography to isolate pure volatile components from complex samples is described. The method was developed through isolation of 1,4-dimethoxybenzene (5.2 mu g. 10 injections) from a peppermint essential oil. Then isomers of 1- and 2-methylnaphthalene were isolated from a complex crude oil in sufficient amounts (3.1 mu g, 38 injections and 5.0 mu g, 35 injections) for discrimination using (1)H NMR spectroscopy. This methodology is applicable to identify any volatile molecule in complex matrices requiring confirmation using NMR spectroscopy.