For the first time, germania-based hybrid organic-inorganic sol-gel materials were developed for analytical sample preparation and chromatographic separation. Being an isostructural analog of silica (SiO2), germania (GeO2) is compatible with silica network. This structural similarity, which is reflected by the relative positions of germanium and silicon in the periodic table, stimulated our investigation on the development of germania-based sol-gel hybrid organic-inorganic coatings for analytical applications. Sol-gel sorbents and stationary phases reported to date are predominantly silica-based. Poor pH stability of silica-based materials is a major drawback. In this work, this problem was addressed through development of germania-based organic-inorganic hybrid sol-gel materials. For this, tetramethoxygermane (TMOG) and tetraethyoxygermane (TEOG) were used as precursors to create a sol-gel network via hydrolytic polycondensation reactions to provide the inorganic component (germania) of the organic-inorganic hybrid coating. The growing sol-gel germania network was simultaneously reacted with an organic ligand that contained sol-gel-active sites in its chemical structure. Hydroxy-terminated polydimethylsiloxane (PDMS) and 3-cyanopropyltriethoxysilane (CPTES) served as sources of nonpolar and polar organic components, respectively. The sol-gel reactions were performed within fused silica capillaries. The prepared sol-gel germania coatings were found to provide excellent pH and thermal stability. Their extraction characteristics remained practically unchanged after continuous rinsing of the sol-gel germania-PDMS capillary for 24 hours with highly basic (pH=13) and/or acidic (pH = 1.3) solution. They were very efficient in extracting non-polar and moderately polar analytes such as polycyclic aromatic hydrocarbons, aldehydes, ketones. Possessing the polar cyanopropyl moiety, sol-gel germania cyanopropyl-PDMS capillaries were found to effectively extract polar analytes such as alcohols, fatty acids, and phenols. Besides, they also showed superior thermal stability compared with commercial cyano-PDMS coatings thanks to the covalent attachment of the coating to capillary surface achieved through sol-gel technology. Their extraction characteristics remained unchanged up to 330°C which is significantly higher than the maximum operation temperature ( < 280 ºC) for commercial cyano-PDMS coatings. Low ng/L detection limits were achieved for both non-polar and polar test solutes. Our preliminary results also indicated that sol-gel hybrid germania coatings have the potential to offer great analytical performance as GC stationary phases.