Quantum chemical calculations using gradient-corrected DFT at the BP86/TZ2P+ level were carried out for the metal–dioxime complexes [M{RC(NOH)C(NO)R} 2 ]with M = Ni, Pd, Pt, R = CH 3 , H, F, Cl, Br, Ph, CF 3 . The nature of the metal–ligand bond was investigated with an energy decomposition analysis (EDA). The complexes with electron donating substituents R = H, CH 3 have the strongest metal–ligand interaction energies ΔE int , as well as the largest bond dissociation energies. The analysis of the bonding situation revealed that the metal ← ligand σ donation is much stronger than the metal → ligand π backdonation. The breakdown of the orbital interactions into the contributions of orbitals with different symmetry indicates that the donation from the in-plane lone-pair donor-orbitals of nitrogen into the d xy AO of the metal provides about one half of the stabilization which comes from ΔE orb . Inspection of the EDA data indicates that the electrostatic term ΔE elstat is more important for the trend of the metal-oxime interactions in [M{RC(NOH)C(NO)R} 2 ] than the orbital term ΔE orb .