Due to their high nutritional value, seeds are often the target of herbivory. In response, plants have evolved a host of adaptations that physically and/or chemically reduce the likelihood of granivory. In grain legumes, the main chemical defences within the endosperm derive from anti-nutritional proteins such as lectins and protease inhibitors. However, less is known about the bioactivity of secondary metabolites found within seeds. Here, solvent extraction was used to identify the major classes of phytochemicals found within the endosperm of both resistant beans (Phaseolus vulgaris) and susceptible beans (Vigna unguiculata). Phenols and terpenoids were recovered from the resistant P. vulgaris seeds only, whilst glycosides and flavonoids were recovered in greater amounts from P. vulgaris in comparison to V. unguiculata. To assess the bioactivity of the extracts against the seed beetle, Callosobruchus maculatus, the extracts were incorporated into artificial seeds and key life-history traits of the beetle determined. The results show the endosperm of both resistant and susceptible beans to contain an ensemble of secondary metabolites that deter oviposition (antixenosis) by adult beetles and disrupt the survival and development of the larvae (antibiosis). However, no extract resulted in complete resistance, indicating that the phytochemicals function alongside other anti-herbivory mechanisms such as α-amylase inhibitors and protease inhibitors. Breeding programmes could potentially select for key phytochemical groups such as terpenoids or glycosides in cultivars in order to optimise the trade-off between resistance and agronomic quality by harnessing the anti-herbivory properties of secondary metabolites in conjunction with anti-nutritional proteins.