Dietary polyphenols are associated with protection against chronic diseases such as cardiovascular disease. Pharmacological studies show a range of bioactivities and efficacy attributable to specific polyphenols. While many fruits are rich in polyphenols, wide cultivar variation of polyphenol composition is common. Our objective was to determine the composition of major bioactive polyphenols in 29 prevarietal selections of Western Australian plums, and Black Amber as an evaluation in developing breeding tools to develop fruit that may have enhanced health-promoting capacities. Total phenolics were quantified colorimetrically; selected polyphenols were quantified by HPLC; and the total antioxidant capacity (TAC) was measured by the antioxidant inhibition of oxygen radicals (AIOR) assay. Total phenolic concentration was significantly correlated with TAC (R = 0.95, P < 0.01). Neo-chlorogenic acid and quercetin glycosides were found to be the predominant polyphenols (mean 29.9 mg·kg(-1) and 50.7 mg·kg(-1), respectively). No significant correlations were found between the composition of predominant polyphenols in plums and the TAC. We argue that the value of in vitro TAC assays to breeding programs may be limited, and future research should focus on the heritability of known bioactive polyphenols.