A novel preparative-scale triple gas chromatographic system, equipped with three Deans-switch devices, is herein described. The isolation of volatile compounds was achieved by using a lab-made collection system. Considerations are made on the possibility to inject high volumes of neat sample, maintaining, at the same time, high resolution levels. The degree of recovery of a series of compounds, characterized by a differing volatility, is also reported. In this respect, different collection conditions were evaluated, namely, the presence (or not) of packing material as well as CO(2) cooling, in various combinations. Finally, the interconnected features, that is time requirements and the isolation of "acceptable" analyte quantities (e.g., milligram level for NMR characterization), are related to parameters such as analyte concentration, injected volume, collection conditions, and number of GC runs. The results herein reported will demonstrate the need for a high-resolution GC step, prior to analyte collection, in the prep-GC analysis of complex samples.