We have studied the crystal structure of a Cu(II) complex [Cu(bbim)(2)]((Pr4N)-Pr-n)(Na). MeOH (1) [where bbim(2-) = di-deprotonated 2,2’-bibenzimidazolate and (Pr4N+)-Pr-n = tetra-n-propylammonium cation] with two bbim(2-) as a di-deprotonated ligand for the first time. The X-ray crystal analysis shows that this Cu(II) complex consists of one-dimensional infinite chains with an alternate bonding sequence of Cu(II) and Na(I) bridged by the bbim(2-) ligand. Interestingly, Cu(II) ion in this complex has a distorted tetrahedral coordination structure. The interaction between these infinite chains is separated by (Pr4N+)-Pr-n cations.