We report the synthesis of α-aminonitriles by one-pot coupling reaction of aldehyde, amines and trimethylsilyl cyanide (TMSCN) using β-ketoiminato zinc complexes as a pre-catalyst in very good yield under mild reaction condition. Homoleptic zinc complex [{κ2-(2,4,6-Me3C6H2NC(Me)=CHC(Me)=O)}2Zn] (1 a) was synthesized by the treatment of protic ligand [(2,4,6-Me3C6H2NHC(Me)=CHC(Me)=O)] (L1H) with potassium hydride and anhydrous zinc diiodide in 2 : 2 : 1 molar ratio in THF. Analogous reactions using [(2,6-iPr2C6H3NHC(Me)=CHC(Me)=O)] (L2H) and [(Ph2CHNHC(Me)=CHC(Me)=O)] (L3H) as protic ligands, dinuclear zinc complexes [{κ3-(2,6-iPr2C6H3NC(Me)=CHC(Me)=O)}ZnI]2 (1 b) and [Zn(Ph2CHNHC−(Me)=CHC(Me)=O)ZnI2] (1 c) were obtained in good yield. Molecular structures of ligands L1H, L3H, and zinc complexes 1 a, 1 b, and 1 c were established by single-crystal x-ray diffraction analysis. Dinuclear zinc complexes 1 b, and 1 c exhibited high transformation, greater selectivity and broad substrate scope for the synthesis of α-aminonitrile under mild condition. A most plausible mechanism for synthesis α-aminonitrile is proposed based on several controlled reactions. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim