<jats:title>Abstract</jats:title><jats:p>The GC‐MS identification of several abundant long‐chain aliphatic <jats:italic>n</jats:italic>‐alkyl caffeates, together with other <jats:italic>p‐</jats:italic>hydroxycinnamic acid esters, in the dichloromethane extracts of the bark of <jats:italic>Acacia dealbata</jats:italic> and<jats:italic> A. melanoxylon</jats:italic>, is reported. In addition, the unambiguous differentiation between two Δ<jats:sup>7</jats:sup>‐steryl glucosides (namely, spinasteryl glucoside and dihydrospinasteryl glucosides) and the homologous Δ<jats:sup>5</jats:sup>‐steryl glucosides was achieved based on the EI‐MS fragmentation features of their trimethylsilyl derivatives. Copyright © 2007 John Wiley & Sons, Ltd.