A laboratory-made fused silica fiber coated with a porous layer of activated charcoal (PLAC) was used as a new microsolid phase in solid-phase microextraction (SPME) mode for sampling of polycyclic aromatic hydrocarbons (PAHs) from the headspace of water samples. Effects of temperature, salt addition, stirring speed, and exposure time on extraction efficiency were investigated. Extraction at 80°C for 30 min in the presence of 12 g NaCl at constant stirring speed yields maximum efficiency. Using the proposed microsolid phase as an efficient sampling device and capillary gas chromatography with flame ionization detection, reliable determination of these compounds at sub-parts-per-billion concentrations was achieved. The calibration graphs were linear in the range 0.1–50 ng/ml and the detection limits were 0.03–0.3 ng/ml. The proposed method was successfully applied to the determination of PAHs in environmental samples such as local municipal water.