Yttria containing hybrid organic-inorganic sol-gels may be used in coatings for capillary microextraction, optionally hyphenated to online HPLC analysis. The sol-gel reaction mixture can use an yttrium trialkoxyalkoxide, such as yttrium trimethoxyethoxide, and a [bis(hydroxyalkyl)-amino-alkyl]-terminated polydialkyl/arylsiloxane, such as [bis(hydroxyethyl)-amine] (BHEA)-terminated polydimethylsiloxane, that can undergo hydrolysis and polycondensation, to form coating materials. Capillaries coated with such sol-gels can have improved extraction efficiency compared, e.g., to pure yttria-based coatings. The CME-HPLC can analyze water samples containing analytes of varied polarity, with excellent extraction of amides, phenols, alcohols, ketones, aldehydes, and polyaromatic hydrocarbons and detection limits ranging from 0.18 to 7.35 ng/mL (S/N=3). Such capillaries can exhibit solvent stability at pH 0 to 14, RSD % between 0.6 to 6.8% (n=3), at a preparative reproducibility RSD between 4.1 and 9.9%.