In this work, the first phytochemical analysis ever performed on the whole cone of Araucaria bidwillii Hook is presented. This was carried out by means of column chromatography, NMR spectroscopy and MS spectrometry on the female cone, evidencing the presence of forty metabolites, thirty-three of which are primary metabolites whilst the remaining are secondary metabolites. A chemophenetic evaluation was also performed reporting seven new compounds for the species. These results are important since they provide more information on the phytochemistry of this species and also underline the need to study more of its populations.