Abstract: In order to develop a method for analyzing the headspace constitutes in tobacco casing No.025, ether extraction and the influence of the conditions of headspace solid phase microextration(SPME)with 100 μm polydimethylsiloxane(PDMS)or 85 μm polyacrylate(PA)fiber tips on the extracted amount of ethyl benzeneacetate, nerolidol and benzyl benzoate in the casing were investigated, and GC/MS analysis was conducted as well.The results showed that:1)24, 17 and 51 compounds were identified in ether, PDMS and PA extraction respectively;2)the optimized SPME conditions of PA were:15 mL casing incorporated with 30% NaCl shaked for 20 minutes at 70℃, extracted with PA for 15 minutes at 90℃, and then desorbed for 2 minutes.