New volatile β-iminoketonate complexes of Ni(L)2 and Pd(L)2 were obtained. β-Aminovinylketone C(CH3)3C(NH2)CHC(O)C(CH3)3 was used as HL. Synthesis of the compound is described, and element analysis, DTA, and IR spectral data are given. The complexes were investigated by XRPA and XRD. The structures are molecular, consist of the trans complexes, and are isostructural. The central atoms have a square plane environment with a (MO2N2) coordination unit. The M-O and M-N distances and the N-M-O valence chelate angles are equal, 1.834 Å, 1.848 Å, and 94.2° for Ni(L)2 and 1.972 Å, 1.975 Å, and 92.4° for Pd(L)2.