New composite adsorbents including silica supports (silica, aerosilogel, and diatomite) and carbon materials (multiwall carbon nanotubes and pyrolytic carbon) have been prepared and characterized. The analytical capabilities of the produced sorbents have been evaluated by their efficiency in the express pre-concentration of volatile organic compounds (butanol and phenols) from the air stream. The prepared surface-layered adsorbents containing multiwall carbon nanotubes placed onto the surface of aerosilogel by use of the carbon vapor deposition method with preloading cobalt nanostructures as a catalyst were found significantly more efficient than traditionally used graphitic carbon-based adsorbents Carbopacks B, C, and X. Additionally, a new adsorbent composed of diatomite Porochrome-3 support coated with a pyrocarbon layer was prepared. This low surface area composited adsorbent allowed both quantitative pre-concentration of phenol and isomeric cresols from the air and their thermal desorption. The developed adsorbents provided fast preconcentration of selected phenols with a concentration factor of 2 × 103 in 5 min and were used for gas chromatographic determination of analytes in the air at low concentration levels starting from several µg/m3 with a flame ionization detector.