The syntheses, structural characterization and magnetic behavior of five new copper(II) polynuclear compounds with formulae [Cu4(μ2-CH3COO)2(μ-bdmap)2(μ1,5-dca)2(dca)2(H2O)2] 1, [Cu2(μ2-CH3COO)(μ-bdap)(μ1,1,5-dca)(μ1,3-dca)]n2, [Cu4(μ2-CH3COO)2(μ-bdmap)2(μ1,1-NCS)2(NCS)2] 3, [Cu2(μ2-CH3COO)(μ-bdap)(NCS)2] 4 and [Cu2(μ1,3-N3)(μ-bdmap)(N3)2]n5 in which bdmapH is 1,3-bis(dimethylamino)-2-propanol, bdapH is 1,3-bis(amino)-2-propanol and dca is the anionic dicyanamide ligand, are reported herein. Tetranuclear complex 1 crystallizes in the monoclinic system, space group P21/n, with unit cell parameters a = 8.284(8), b = 21.52(1), c = 11.432(3) Å, β = 105.19(2)°, Z = 2. Bi-dimensional complex 2 crystallizes in the triclinic system, space group P, with unit cell parameters a = 8.184(5), b = 8.792(2), c = 10.887(2) Å, α = 75.65(2), β = 76.55(3), γ = 74.36(3)°, Z = 2. Tetranuclear complex 3 crystallizes in the triclinic system, space group P, with unit cell parameters a = 8.455(4), b = 9.114(9), c = 12.744(8) Å, α = 104.62(8), β = 99.86(6), γ = 106.10(8)°, Z = 1. Dinuclear complex 4 crystallizes in the triclinic system, space group P, with unit cell parameters a = 8.15(1), b = 8.18(2), c = 11.44(1) Å, α = 69.39(2), β = 80.36(2), γ = 80.37(2)°, Z = 2. One-dimensional complex 5 crystallizes in the orthorhombic system, space group P212121, with unit cell parameters a = 20.45(4), b = 11.36(3), c = 6.43(1) Å, Z = 4. The magnetic behavior of all the complexes has been checked giving a bulk antiferromagnetic coupling in all the cases with |J| values in the range 109–144 cm−1 for 1–4. Compound 5 is diamagnetic in the 2–300 K range of temperatures. The found J values for 1–5 can be justified from the structural data taking into account the orbital countercomplementarity for 1–4 and the orbital complementarity for 5.