A novel solid-phase microextraction (SPME) fiber was prepared by coating an HPLC β-cyclodextrin bonded silica stationary phase (CDS) on the surface of a fused-silica fiber. The fiber was evaluated for the determination of five phenol compounds (phenol, 2,4-dimethylphenol, 4-nitrophenol, 3-chlorophenol, 4-methylphenol). Compared with commercially available polymer coatings, the CDS coating showed high sensitivity and fast velocity of mass transfer for phenol compounds because of its porous structure and a unique molecular structure of β-cyclodextrin. In addition, the CDS coating was proved to be very stable at a relatively high temperature (up to 300℃). The method was suitable for the determination of phenol compounds in aqueous samples. The determination of 4-nitrophenol in soil by microwaveassisted extraction (MAE) coupled to solid-phase microextraction was also investigated.