The GC-MS identification of several abundant long-chain aliphatic n-alkyl caffeates, together with other phydroxycinnamic acid esters, in the dichloromethane extracts of the bark of Acacia dealbata and A. melanoxylon, is reported. In addition, the unambiguous differentiation between two delta7-steryl glucosides (namely, spinasteryl glucoside and dihydrospinasteryl glucosides) and the homologous delta5-steryl glucosides was achieved based on the EI-MS fragmentation features of their trimethylsilyl derivatives.