This review article focuses on advances and technical developments of the realm of membrane extraction techniques for the analytes that are (made) amenable to gas chromatographic analysis, and sheds light on the analytical applications to biological and environmental samples. In this review, the state of the art in this growing area of membrane extraction for gas chromatography is presented and several selected examples from our work and that of other groups are discussed. The published articles on the techniques and their applications, found in the scientific literature between the years 2000 and May 2007 and cited in over than 100 references, are perused and commented. A good deal of light will be thrown on the novelty of the techniques, instrumentations and applications. The mentioned techniques are mainly microporous membrane liquid-liquid extraction, extracting syringe, two-phase hollow-fibre-protected liquid-phase microextraction and its modifications, and membrane extraction with sorbent interface and its variants. The merits and demerits of the techniques will be highlighted.