This study examines the macroscopic appearance of selected members of the Araucariaceae and investigates 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 analyzed statistically using supervised and unsupervised classification algorithms. Results indicate that A. araucana can be distinguished from the look-alike taxa.