Electronic cigarettes（e-cigarettes） are popular nicotine delivery devices. e-cigarette liquid is a complex mixture of ingredients with a viscous base，in addition to the propylene glycol（PG），vegetable glycerin（VG） and flavorings，illicit drugs are often added. Testing for glamorous flavors and illicit drugs in e-cigarettes is a common request from health surveillance，forensic science and market regulation. In this work，we have combined thin-film solid-phase microextraction with a simple gas chromatography-mass spectrometry method. The established method realized the micro-total analysis of low-boiling-point flavors and high-boiling-point illicit drugs in headspace of e-cigarettes. A polystyrene-divinylbenzene particle-loaded membrane was prepared by coating. The sampling conditions of flavors and illicit drugs were optimized，and the optimal extraction condition was 30 min at 180 ℃. All the compositions in the headspace of e-cigarettes showed acceptable accuracy. Thermal desorption experiments of membranes were further explored and the results obtained complemented with solvent extraction desorption. However，considering the real case handling situation，solvent extraction was chosed as desorption method for establishing the e-cigarette analytical methods. At the same time，thermal desorption method enriches the selection space for handling e-cigarette related samples. Compared with conventional direct dilution injection and commercial solid-phase microextraction fibers，this method enhances the analytical sensitivity by expanding the adsorption capacity，improving the universality by removing VG and PG. In addition，it is suitable for high-temperature extraction and has the advantage of low cost. Lastly，the proposed method was applied to three seized e-cigarette which results were consistent with the case intelligence，verifying the accuracy of this method. This work provides an efficient and accurate micro-total analytical protocol for flavors and illicit drugs in headspace of e-cigarette，which is important for health，forensic science and the public environment.