Ergosine showed the highest tendency to epimerize while ergometrine proved to be the most stable compound among the ergot alkaloids investigated. It has been reported that the epimerization of ergot alkaloids is minimal when standard solutions are prepared in aprotic solvents such as chloroform or acetonitrile. However, the use of a sample solvent that is stronger than the mobile phase leads to peak distortion. A careful investigation of different solvent mixtures indicated that a sample solvent consisting of methanol/acetonitrile/water (20/40/40, v/v/v) delivers a good peak shape while keeping the epimerization negligible. Finally, it was shown that by using this sample solvent, maintaining the autosampler temperature at 4 °C and limiting the sample sequence to a maximum of 24 h, no epimerization occurred during the LC–MS/MS analysis (data not shown)