A novel solid phase microextraction coating that contains perhydroxy cucurbit[5] uril was prepared by a sol-gel method. With 3-(2-cyclooxypropoxyl) propyltrimethoxysilane as cross-linking agent, perhydroxyl cucurbit[5] uril(Q[5](OH)10) and hydroxy-terminated poly(dimethylsiloxane)(OH-PDMS) were used as starting coating material to bond chemically to a fused-silica substrate to form a PDMS/Q[5](OH)10 coating by hydrolysis and polycondensation reactions. The surface morphology, microstructure and thermal stability of the obtained composite coating were characterized by scanning electron microscopy(SEM),Fourier-transform infrared spectrometry(FTIR),differential scanning calorimetry(DSC) and thermogravimetric(TG) analysis. The results showed that the coating has a large specific surface area, high thermal stability(360℃) and long lifetime. Its performance was tested using a homemade solid-phase microextraction coating fiber coupled with gas chromatography-mass spectrometry(GC-MS) to analyze volatile components in Rosmarinus officinalis L(ROL).The optimized solid-phase microextraction conditions included an extraction temperature of 80℃,an extraction time of 45 min and a 0.2000g sample. The volatile components were extracted by head solid-phase microextraction(HS-SPME) with a homemade extraction fiber, and identified by GC-MS. The relative content of each component was determined by area normalization. Twenty-five compounds in the ROL were identified. The main compounds are 1,8-cineole,camphor and α-pinene. The homemade fiber was compared with commercial fiber(PDMS/DVB/CAR).According to the quantity and content of the extracts from ROL, the extraction effect of the two kinds of fiber are equivalent, which indicated that the homemade novel fiber could be applied in the rapid detection of volatile components in plants.