As a contribution to the occurrence of ergot alkaloids in ergot from German rye and triticale, samples from the 2007 and 2008 harvests were analyzed. Twelve alkaloids—six pairs of main alkaloids and their corresponding epimers—were determined in extracts prepared under alkaline conditions by HPLC with fluorescence detection without preceding purification. The total alkaloid content was found to be 0.03–0.18% in ergot from rye (n = 19) and 0.06–0.22% in ergot from triticale (n = 4), respectively. Furthermore, single sclerotia (n = 40) were investigated in terms of alkaloid content and distributional pattern. The main alkaloids in ergot were ergocristine, ergotamine and ergocornine, although the alkaloid composition was highly variable.