A sample enrichment probe (SEP) consisting of a thin rod of an inert material and provided at one end with a short sleeve of polydimethylsilicone rubber was used for the high-capacity sample enrichment of analytes from gaseous and aqueous samples for analysis by gas chromatography (GC) and its hyphenated techniques. The silicone rubber was exposed to the analytical sample, after which the end of the rod carrying the silicone rubber was introduced into the injector and the analytes thermally desorbed and analysed by GC. This technique is similar to, but differs from, solid-phase microextraction (SPME) in that a much larger volume of the sorptive phase is employed, the sorptive phase is not introduced into the inlet of the GC via a needle and the injector is opened to the atmosphere for the introduction and removal of the SEP. In the determination of volatile and semi-volatile organic compounds in gaseous and aqueous media, the SEP technique gave results comparable with those obtained by the stir-bar-sorptive extraction (SBSE) and high-capacity sorption probe (HCSP) techniques. Implementation of the SEP technique requires only minor adaptations to the gas chromatograph and does not require any auxiliary thermal desorption and cryotrapping equipment.