A zwitterionic amine bridged bis(phenolate) ytterbium(III) complex was synthesized, and its reactivity with a zinc cluster was explored. The reaction of (C5H5)3Yb(THF) with the amine bridged bis(phenol) HONNOH [ONNO = Me2NCH2CH2N{CH2-(2-O-C6H2-But2-3,5)}2] in a 1:2 M ratio in toluene at 80 °C produced the zwitterionic ytterbium complex [ONNO]Yb[ONNO(μ4-H)] (1) in a high isolated yield. The reaction of ZnEt2 with 1 equiv of PhCH2OH gave a zinc cluster Zn7Et6(OCH2Ph)8 (2) in a good isolated yield. Complex 1 reacted with complex 2 in a 7:1 M ratio at room temperature to afford the unexpected ligand redistributed product [ONNO]Zn(THF) (3). These complexes were well characterized by elemental analyses, IR spectra and NMR spectroscopy in the case of complexes 2 and 3. The definitive molecular structures of complexes 2 and 3 were determined by single-crystal X-ray analyses.Graphical abstractA new method to approach the zwitterionic amine bridged bis(phenolate) lanthanide(III) complex has been provided, and the reactivity of the zwitterionic ytterbium complex toward a zinc alkyl cluster has been explored.Highlights► A new approach to synthesizing zwitterionic lanthanide complex was provided. ► The reactivity of the zwitterionic lanthanide complex was explored. ► A novel alkylzinc alkoxo cluster was characterized.