A group of new compounds with the general formula Cu(L)(sol(-))(A(-))(Hsol), where A = ClO4-, CF3SO3-, BF4(-), and NO3-, L = bis(2-benzimidazolyl)propane (abbreviated as tbz) and bis(2-benzimidazolyl)butane (abbreviated as qbz), and Hsol = methanol and ethanol, and with the formula [Cu(tbz)(N-3(-))(Hsol)] has been prepared and characterized structurally, magnetically, and spectroscopically. Three representative compounds [CU2(tbZ)(2)(CH3O)(2)](ClO4)(2)(CH3OH)(2) (1), [CU2(tbz)(2)(NO3)(CH3O)(2)](NO3)(CH3OH)(2) (5), and [Cu(tbz)(N-3)(2)](2)(CH3 OH)(2) (13) were characterized structurally with X-ray diffraction. Crystal data for 1 : monoclinic, space group P2(1)/c with a = 9.6863(10) Angstrom, b = 12.9445(10) Angstrom, c = 19.394(2) Angstrom, beta = 113.259(10)degrees, and Z = 2. Crystal data for 5 : monoclinic, space group P2(1) with a = 9.5497(6) Angstrom, b = 12.5073(7) Angstrom, c = 17.5920(12) Angstrom, beta = 90.996(6)degrees, and Z = 2. Crystal data for 13 : orthorhombic, space group Pbca (No. 61) with a = 11.3325(7) Angstrom, b = 18.7096(16) Angstrom, c = 19.2011(16) Angstrom, and Z = 4. The structure refinement converged to wR2 = 0.1381, R1 = 0.0534 for 1, wR2 = 0.0674, R1 = 0.0271 for 5, and wR2 = 0.1119, R1 = 0.0701 for 5. The structures 1 and 5 consist of dinuclear units with bridging methoxo groups and one ligand linked to each copper via the N, re 5 consists of a dinuclear unit in which one of the copper atoms is linked to a nitrate O, to yield a unit with two different copper environments, one square planar and the other square pyramidal.