This study focuses on the synthesis and characterization of heptanuclear iron(III) compounds featuring polyalcoholamine ligands. Ultrasonic treatment of small trinuclear or hexanuclear pivalate clusters and diethanolamine derivatives (R-deaH2, R = CH3 (1); CH3C6H4 (2)) resulted in two heptanuclear iron(III) clusters with general formula [Fe7O2(piv)9(R-dea)3(H2O)3]. A single-crystal X-ray diffraction analysis shows that clusters 1 and 2 have a disk-like {Fe7O3} core in which the central FeIII atom linked to FeIII 6 hexagon by three μ3-O2− groups. Six pivalates and three polyalcoholamine ligands additionally bridge all FeIII atoms. The remaining pivalates and three water molecules completed the coordination sphere of metal atoms. In summary, this study showcases the synthesis and characterization of heptanuclear iron(III) compounds with amine alcohol ligands, offering a deeper understanding of their structural properties, with promising implications for the field of coordination chemistry and advanced materials science.