A simple, convenient, and highly efficient preparative GC system has been developed that uses short sections of megabore capillary columns as sample collection (sorbent) traps. The performance of this system with various types of capillary column traps and under various collection conditions was systematically investigated with model compounds, including C4 to C20 normal alkanes, esters, and alcohols. The thickness and polarity of the sorptive stationary phase and the temperature of the collection trap affected trap performance. Each group of compounds was efficiently trapped above a critical Kovat's index, and the type of trap (deactivated, methyl polysiloxane, polyethylene glycol), film thickness, and whether or not the trap was cooled significantly shifted this threshold index. Above this critical index, recovery efficiencies of traps with methyl polysiloxane films were 80-100% for a wide range of injected sample mass. For example, a DB-1 collection trap with a film thickness of 1.5 microm methyl polysiloxane operated at ambient temperature trapped >84% of the mass of injected compounds of all three chemical classes with Kovat's index >1,100 (determined on a nonpolar column) with injected sample mass ranging from 10 to 1,000 ng of each compound. This preparative GC system is technically and economically feasible for most researchers. Furthermore, it is suitable for the preparation of NMR samples of volatile and semivolatile compounds, especially with sample sizes ranging from several nanograms to several micrograms.