In order to selectively analyze polycyclic aromatic hydrocarbons (PAHs) from various complex samples, a type of new and stable solid phase microextraction (SPME) with layered graphene / polydimethylsiloxane phase has been designed and fabricated to utilize the strong π-stacking interaction.The graphene-based SPME was validated to be effective in gas chromatography-mass spectrometry (GC-MS) of PAHs (Figure 1).Because the graphene is a double-sided polyaromatic scaffold with an ultrahigh specific surface area (theoretical value 2630 m2/g) or high loading capacity [1], the SPME can offer quiet a high sensitivity, with a limit of detection down to 5.1-15.5 ng/L PAHs.The new SPME was also shown to be stable and reproducible, capable of being repeatedly used for 80-120 extraction/desorption cycles.It has been applied to the determination of PAHs in tobacco smokes, natural vapor of asphalt construction (such as highways) and some biofluids.Detailed discussion will be presented on the conference.