ZnO　nanorod　array　coating　is　a　novel　kind　of　solid-phase　microextraction　(SPME)　fiber　coating　which　shows　good　extraction　capability　due　to　the　nanostructure.　To　prepare　the　composite　coating　is　a　good　way　to　improve　the　extraction　capability.　In　this　paper,　the　ZnO　nanorod　array　polydimethylsiloxane　(PDMS)　composite　SPME　fiber　coating　has　been　prepared　and　its　extraction　capability　for　volatile　organic　compounds　(VOCs)　has　been　studied　by　headspace　sampling　the　typical　volatile　mixed　standard　solution　of　benzene,　toluene,　ethylbenzene　and　xylene　(BTEX).　Improved　detection　limit　and　good　linear　ranges　have　been　achieved　for　this　composite　SPME　fiber　coating.　Also,　it　is　found　that　the　composite　SPME　fiber　coating　shows　good　extraction　selectivity　to　the　VOCs　with　alkane　radicals.