Rye ergot (Claviceps purpurea) occasionally causes toxicity (chiefly expressed as hyperthermia) in Australian livestock, either as a result of grazing infected annual (Lolium rigidum) and perennial (L. perenne) rye grasses, or if the ergot sclerotia produced in rye grasses contaminate grain crops used as stockfood. Alkaloids in 30 samples of Australian rye ergot sclerotia taken from rye grasses and grain screenings, and some feed samples contaminated with rye grass ergot sclerotia, were assayed by high performance liquid chromatography. Samples originated from across southern Australia. Ergotamine was the dominant alkaloid in all samples, followed by α-ergocryptine, ergocornine, ergosine and their respective -imine epimers. Ergotamine concentrations in sclerotia ranged up to 2257 mg/kg (as received basis). Ergocristine was a very minor component (<50 mg/kg) in all samples. Total alkaloids in freshly collected sclerotia ranged from 1003 to 3321 mg/kg (0.10 to 0.33%), and up to 3766 mg/kg with epimers included, although lower concentrations were found in samples stored for some time. Alkaloid profiles in sclerotia were all very similar, and concentrations did not appear to be related to size of sclerotia, source region, nor to the rye grass or grain from which they were taken. Previous cases of toxicity in livestock are reviewed and several new cases are reported. The implications of variable alkaloid contents of rye ergot sclerotia are discussed in terms of Australian food and stockfeed regulations.