Metergoline is a dopamine agonist and serotonin antagonist used both in human and veterinary medicine. In addition to the previously known crystalline form, a new polymorph, which crystallizes from aqueous solution, was found. Since it was initially impossible to prepare a single crystal of quality suitable for single crystal X-ray diffraction measurements using a conventional laboratory source, the structure was solved from the powder diffraction data using synchrotron radiation. The structure determination also included solving the effects of preferred orientation. Characterization was simultaneously done by solid-state NMR spectroscopy. Finally, a small single crystal suitable for synchrotron diffraction was found after numerous tries. Crystal structure determination using this single crystal confirmed the powder-based solution. Comparison of information obtained by different experimental methods (powder diffraction, ssNMR, single crystal diffraction) was made.