The structures of three new Cu(II) complexes with pyridine carboxamide ligands (Me 2 bpb, 6-Me 2 -Mebpb, and 6-Me 2 -Me 2 bpb) have been determined. 6-Methyl-substituted pyridyl bpb ligands produced dimeric compounds with Cu(II) ions, and weak interactions between dimers can make even polymeric compounds, while bpb ligands without 6-methyl substitution produced monomeric Cu(II) complexes. The large distortion effects of 6-methyl-substitution are shown in Cu(II) complexes with 6-methyl-substituted pyridyl bpb ligands. This result suggests that the steric effect of 6-methyl-substitution plays important role for distortion of the structure, and 6methyl-substitution can also influence to make polymeric compounds with interactions between Cu(II) ions and neighbor carbonyl oxygen atoms. In addition, the voltammetric behaviors of the Cu complexes were examined and classified into two groups, with/without 6methyl group. The complexes without 6-methyl group show reversible redox waves at $ร1.6 V, and the complexes with 6-methyl group do irreversible redox ones at $ร1.3 V, indicating that the presence of the methyl group of 6-position of the complex makes the reduction of the complexes easier.