The mixed-ligand picolinato (pic) complex of Cu(II) with 4-methylimidazole (4-MeIm), [Cu(pic)2(4-MeIm)2], was synthesized and characterized by elemental analysis, magnetic susceptibility, spectroscopic methods (UV/vis and FT-IR) and X-ray diffraction. In the slightly distorted octahedral cis-bis(4-methylimidazole)bis(picolinato)copper(II) complex, the pic ligands are coordinated to the Cu(II) ion as bidentate N, O-donors forming chelate rings. The 4-MeIm ligands are N-coordinated in cis positions. The complex crystallizes in the triclinic space group P1 with unit cell parameters a = 9.204(5), b = 9.498(5), c = 13.095(5) Å, α= 90.395(5), β = 101.687(5), γ = 112.291(5)° and Z = 2. Hydrogen bondings and C-H⋯π interactions occur between picolinato and methylimidazole ligands of neighboring complex molecules. The thermal decomposition of the complex is described. © 2006 Verlag der Zeitschrift für Naturforschung.