The first successfully developed molecularly imprinted polymer toward six ergot alkaloids and their respective epimers is described. A new imprinting molecule, metergoline, was used as template analogue in the production of suspension polymerized beads. These spherical particles functioned as selective sorbent in a solid-phase extraction column. The application of this column in the cleanup of barley samples prior to liquid chromatography coupled with tandem mass spectrometry allowed simple and cost-efficient sample preparation. The performance of the imprinted polymer and a non-imprinted control polymer was evaluated. This includes determination of the recovery values and the matrix effect of each of the 12 tested ergot alkaloids as well as a cross-reactivity study with 25 common mycotoxins. The binding isotherms were obtained for metergoline, thus allowing comparison with other (imprinted) sorbents. A comparison between bulk and suspension polymerization is provided to determine the appropriate production technique.