Psychoria viridis (chacruna) is a hallucinogenic plant with psychoactive properties associated with the presence of N,N-dimethyltryptamine (DMT). This species is primarily known as an ingredient of the beverage Ayahuasca, but dry leaves are also smoked by recreational users. The plant is controlled in Poland and France and its proper identification poses many challenges due to the fact that genus Psychotria is relatively large and there are other species that are easily confused with chacruna. The aim of the present work was to develop an effective authentication procedure for the dried and shredded leaves of P. viridis, to be used in comparison of chemical and botanical characteristics of its commercial products. Dried leaves of P. viridis originating from Brazil, Peru and Hawaii were purchased from Internet providers. For DMT identification, thin layer chromatography (TLC) and high performance liquid chromatography (HPLC) methods have been elaborated, validated and applied. In order to clarify the existing differences among samples, chemometric methods have been used. Botanical features and the gas chromatography tandem mass spectrometry (GC-MS) chromatograms have been analyzed using hierarchical cluster analysis (HCA). Our studies revealed significant variety among plant material marketed as P. viridis. Grouping of samples based on their micromorphology features and GC-MS results did not correspond well with the presence of DMT. Based on our results an indisputable identification of dried specimens as P. viridis is very problematic. It is necessary to postulate changes in legislation regarding regulation of P. viridis and replace it with DMT as controlled substance.