The global drug abuse scene is dynamic. After COVID-19 psilocin-containing mushrooms (PCM) reemerged in the international scenario. To identify illicit drugs, multiple analytical methods must be employed including triage (e.g. colorimetric test) and confirmatory tests (e.g. GC-MS). In addition, in many cases, only samples that give positive results in the triage method are taken to the confirmatory ones. However, colorimetric methods have several drawbacks in the analysis of complex unusual samples, such as the PCM, which can produce falsenegative results. This study evaluated the feasibility of the ambient ionization technique direct analysis in real time - high-resolution mass spectrometry (DART-HRMS) as a triage method for the identification of PCM seized samples. A psilocin standard, edible mushrooms, and 5 seized PCM samples were used to establish the DARTHRMS instrumental setup required for psilocin analysis. The developed DART-HRMS method was compared to the triage method recommended for PCM screening analysis (Erlich's test). While the analysis of psilocin solutions applied 300 V at the DART grid and carrier gas at 150 degrees C, the analysis of solid samples applied 300 V and 375 degrees C. All seized PCM samples presented negative results in Erlich's test, while all of them were positive for psilocin by DART-HRMS. Based on the quality of the HRMS data it was possible to confirm that Erlich's test results were false-negative for the seized samples. DART-HRMS presents itself as a fast, reliable, and trustworthy triage method for the qualitative identification of raw hallucinogenic mushrooms for criminal investigation.