An innovative chromatographic analysis was developed for the determination of moniliformin (MON). Because of its ionic nature, MON is weakly retained in reversed-phase chromatography and the separation may be tricky. Nevertheless, this technique is normally used either with the formation of ion pairs or employing specific RP columns for polar compounds, or combining anion exchange and hydrophobic interactions. Hydrophilic interaction chromatography (HILIC) was also used, but a non-negligible peak tailing was observed. Besides its ionic nature, MON is a di-ketone and di-ketones, mainly β-di-ketones, can easily form complexes with lanthanide ions. Then, in this work the addition of lanthanide ions to the mobile phase was investigated, aiming at improving peak shape and MON separation. La, Tb or Eu aqueous solutions were used as mobile phase and MON was chromatographed using a LC-NH column. The probable formation of coordination complexes lanthanide-MON in the HPLC mobile phase allowed to obtain a symmetrical peak shape and a satisfactory chromatographic separation by both mass spectrometry (MS/MS) and UV detection. Finally, a suitable extraction and purification method for MON determination in cereal samples was developed.