A needle-type sample preparation device packed cyclohexanone-coated fibers as an extraction medium has been developed for the gas chromatographic (GC) analysis of volatile amines in air samples. For a simultaneous derivatization/extraction of monoethanolamine (MEA), a fiber-packed needle was employed, where a bundle of heat resistant filaments, Zylon, poly(p-phenylene-2,6-benzobisoxazole) was packed longitudinally into the specially-designed needle. To the needle-type device, cyclohexanone was loaded in the preconditioning process. Gaseous MEA was sampled by a vacuum air sampler connected to the needle, and a simultaneous derivatization/extraction was carried out therein. Desorption of MEA derivative was successfully made at a heated GC injection port without using any desorption solvent. Introducing the simultaneous derivatization with cyclohexanone, the sensitivity was significantly improved, allowing a more sensitive detection of volatile amines. Taking advantage of the specially-designed needle, the needle was able to be stored for several days at room temperature after the sampling, where the derivatives of the volatile amines were stably trapped on the surface of the Zylon filaments in the needle.