In a continuation of studies on Australian Rutaceous plants, two new heraclenol derivatives (2'-O-propionyl-heraclenol and brachycalyn) and 22 known coumarins were isolated from the leaves and twigs of Phebalium aff. brachycalyx. Their structures were determined using spectral data (UV, IR, MS, 1H and 13C NMR, including 2D experiments). All secondary metabolites belong to the coumarin series, consistent with the chemical homogeneity of the genus Phebalium. The chemical composition is closely related to other western species of Phebalium sect. Phebalium. Some compounds (isogosferol, heraclenol monoacetate, 8-[(E)-6-hydroxy-3,7-dimethylocta-2,7-dienyloxy]psoralen) are reported for the first time from the Rutaceae, and others (7-O-prenylumbelliferone, isomeranzin, auraptenol, xanthotoxol, isoheraclenin, 8-hydroxyxanthyletin) are first reported from a Phebalium species.