Determining the species source of logs and planks suspected of being Araucaria araucana (Molina) K.Koch (CITES Appendix I) using traditional wood anatomy has been difficult, because its anatomical features are not diagnostic. Additionally, anatomical studies of Araucaria angustifolia (Bertol.) Kuntze, Araucaria heterophylla (Salisb.) Franco, Agathis australis (D.Don) Lindl., and Wollemia nobilis W.G.Jones, K.D.Hill & J.M.Allen have reported that these taxa have similar and indistinguishable anatomical characters from A. araucana. Transnational shipments of illegal timber obscure their geographic provenance, and therefore identification using wood anatomy alone is insufficient in a criminal proceeding. In this study we examine the macroscopic appearance of selected members of the Araucariaceae and investigate whether analysis of heartwood chemotypes using Direct Analysis in Real Time (DART) Time-of-Flight Mass Spectrometry (TOFMS) is useful for making species determinations. DART TOFMS data were collected from 5 species (n =75 spectra). The spectra were analyzsed statistically using supervised and unsupervised classification algorithms. Results indicate that A. araucana can be distinguished from the look-alike taxa. Another statistical inference of the data suggests that Wollemia nobilis is more similar and within the same clade as Agathis australis. We conclude that DART TOFMS spectra can help in making species determination of the Araucariaceae even when the geographic provenance is unknown.