Two copper(II) complexes, [Cu(L)(N-3)(2)]MeOH and [Cu(L)(NCS)(2)]MeOH, were prepared and characterized by spectroscopic, analytical, and quantum chemical studies, where L is 2,6-bis(1-butylbenzimidazol-2-yl)pyridine. X-ray quality crystals of [Cu(L)(N-3)(2)]MeOH were obtained by slow evaporation of MeOH solution of the complex. Molecular structure of [Cu(L)(N-3)(2)]MeOH was determined by X-ray crystallography. The asymmetric unit contains one [Cu(L)(N-3)(2)] and one MeOH molecule. Cu(II) in [Cu(L)(N-3)(2)]MeOH is five-coordinate, bonded to five nitrogens (three from L and two from two azide anions). Coordination geometry around Cu(II) center is distorted square-pyramidal with value of 0.065. Optimized geometries, IR spectra, and non-linear optical properties of the complexes were obtained by computational studies based on density functional theory (DFT) with M062X method. NLO properties of these complexes were investigated computationally and both complexes exhibit better NLO properties than urea.