Illegal drug smugglings and crimes have long been a global concern, and an apparatus which can identify drugs on-the-spot is urgently demanded by law enforcement. A thermal desorption acetone-assisted photoionization miniature ion trap mass spectrometer was developed for on-site and rapid identification of illegal drugs at checkpoints. Acetone was chosen for dopant-assisted photoionization, and the sensitivity of selected drugs was further enhanced with protonated analyte molecular ions [M + H]. For example, the sensitivity of ephedrine was improved by as high as 22-fold. The mass discrimination effect, which was usually considered as a shortcoming of ion trap mass analyzer, was ingeniously utilized to eliminate the protonated acetone reagent ions and maximize the trapping efficiency of analyte ions in mass analyzer. Twenty-seven drugs were analyzed, and the limits of detection (LODs) of selected illegal drugs were at the nanogram level with analysis time of 2 s. Analyte/dopant ion peak intensity ratios in mass spectra could be used for quantitation to improve the quantitative analysis performance of miniature ion trap mass spectrometer equipped with a discontinuous atmospheric pressure interface (DAPI) with the prerequisite that dopant ions and analyte ions could be simultaneously and effectively trapped by the ion trap. The RSD of signal intensity was reduced from 25.3% to 8.5%, and the linear range was extended from 0.5-25 to 0.5-100 ng/μL for methamphetamine. A temperature-resolved thermal desorption sampling strategy was developed and used to distinguish illegal drug components in plant-based drug samples and drinks containing illegal drugs.