TD-IMS provided spectra of the different Cannabis chemotypes, both in the positive and negative ionization modes, however, it was difficult to distinguish them only by visual inspection of the spectra. To solve this, PCA-LDA was performed, thus being able to group the extracts in different clusters according to the previously defined chemotypes, as well as their psychoactivity and major cannabinoids groups, in both ionization modes. On the other hand, in order to evaluate potential false positive results, non-Cannabis plants were also analyzed and clustered in a different group, therefore demonstrating the potential of the developed methodology for Cannabis discrimination. Additionally, the direct measurement of the plant material was also performed, obtaining separated groups according to the pre-established chemotypes. To study the potential of this approach for drug control, the residues of plants on the fingers of the analysts after being in contact with Cannabis plants were measured as well, obtaining similar characteristic signals to those for plant extracts, with some slight shifts and higher intensity in the positive mode, and more complex spectra in the negative mode (which could be indicating the potential detection of other polar phytochemicals).