Poly (methylphenylvinylsiloxane) (PMPVS) coating for solid-phase microextraction (SPME) was first prepared by using sol-gel approach and cross-linking of free radical initiation. The extraction properties of the novel coating for aromatic compounds were investigated using a self-made SPME device coupled with a gas chromatograph-flame ionization detector (GC-FID). The coating provided high surface areas and allowed high extraction efficiency. Compared with some commercial SPME stationary phases, the new phase showed better selectivity and sensitivity toward aromatic compounds. Furthermore, PMPVS coating showed good thermal stability and longer lifetime.