5,11,17,23-Tetra-tert-butyl-25,27-diethoxy-26, 28-dihydroxycalix[4]arene/hydroxy-terminated silicone oil coated fiber was first prepared and applied for solid-phase microextraction (SPME) with sol-gel technology. The possible sol-gel mechanism was discussed and confirmed by IR spectra. It showed wonderful selectivity and sensitivity to polar (aromatic amines), nonpolar (benzene derivatives, polycyclic aromatic hydrocarbons) and high boiling point compounds (phthalates) and the extraction equilibria were reached quite fast. The coating has high thermal stability (380degreesC) and solvent stability (organic and inorganic), thus its lifetime is longer than conventional fibers. In addition, it has surprising fiber-to-fiber and batch-to-batch reproducibility. The detection limits were quite low and the linear ranges were pretty broad for all analytes. (C) 2003 Elsevier B.V. All rights reserved.