Mesoporous materials were employed as fast, sensitive and efficient fiber coatings of solid-phase microextraction (SPME) for the first time. Three micrometer as-synthesized C16-MCM-41 particles were immobilized onto stainless steel wire with 100 mcoating thickness. In combination with high performance liquid chromatography (HPLC), extraction efficiency and selectivity of C16-MCM-41 were investigated using aromatic hydrocarbons. Effect of extraction and desorption time, extraction temperature, stirring rate and ionic strength on extraction efficiency were examined. Aanalytical merits of SPME with C16-MCM-41 coating were evaluated. The chromatographic peak area is proportional to the concentration of anthracene in the range 0.5-150g 1−1. The limit of detection was 0.05g 1−1 (S/N=3) and the relative standard deviation (R.S.D.) was 0.033%. © 2003 Elsevier B.V. All rights reserved.