Gas chromatography (GC) is one of the most versatile separation methods for volatile compounds, and a variety of polymeric materials as the stationary phases have been developed for various applications. In contrast to the successful applications and commercialization of the polymer-coated columns, the reports for the fibrous polymer-packed stationary phases, however, were quite limited except for the surface characterization of the fibers in the inverse GC (IGC) method. The IGC technique is basically based on the observation of a specific interaction between the fiber surface and the standard solute molecules injected as the sample probes. Therefore, it is natural that a synthetic fiber can be used as a stationary phase material in GC separations, if the fiber possesses both the thermal stability and resistance to the gaseous chemical species throughout the column. Regarding the use of fibrous materials as the stationary phase in liquid phase separation methods, the authors have already reported the use of fibrous cellulose acetate stationary phase in microcolumn liquid chromatography (LC) and capillary electrochromatography (CEC)[1-4]. From the results it was confirmed that the fibrous polymer could play a role as the stationary phase in the chromatographic process. Miniaturized sample preparation with fibrous extraction medium has been also reported, where several hundreds of polymeric filaments were longitudinally packed into a short capillary to prepare the extraction device[5-13]. Based on the above successful applications of fibrous materials as the stationary phase and the extraction medium in the liquid phase separations, fiber-packed capillaries have been introduced for the separation of volatile compounds in GC. The results also showed promise for fibrous material as the stationary phase in GC, especially as the packing material for a short column having a large sample loading capacity[14-16].