A novel poly(dimethylsiloxane)/β-cyclodextrin (PDMS/β-CD) coating was prepared for solid-phase microextraction (SPME) in the form of membrane instead of fiber. The surface of the membrane was uniform and has not gel cracking after dipped into methanol, acetonitrile and acetone. Non-polar polycyclic aromatic hydrocarbons (PAHs) and polar phenolic compounds were used to evaluate the character of the PDMS/β-CD solid-phase microextraction membrane by direct extraction and solvent desorption, followed by GC-MS analysis. Parameters that affect the membrane extraction process were investigated, which included the matrix of sample, extraction time, desorption solvent and time. For PAHs, the linearitywas from 0.10 to 1000μg1-1. The limit of detection (LOD)was in the range of 0.01-0.2μg1-1. The repeatability was in the range of 5.4-9.3%. For phenolic compounds, the linearity was from 0.10 to 5000μg1-1 and LOD varied from 0.02 to 1.5μg1-1. Compared with the SPME fiber, the SPME membrane has a large extraction capacity, low cost of preparation. The sensitivity can be further increased by developing large-volume-injection or thermal desorption technique.