Two μ2-terephthalate (tp) bridged complexes, [Cu2(tp)(pren)4](ClO4)2 (pren = 1,3-diaminopropane) (1) and [Ni2(tp)(pren)4(Him)2](ClO4)2 (Him = imidazole) (2), have been synthesized and characterized by X-ray single-crystal structural analysis. In the discrete dinuclear [Cu2(tp)(pren)4]2+ cation of complex (1), each CuII atom has a square-pyramidal geometry, being coordinated by four nitrogen atoms (avg. 2.031 A) from two pren ligands at the basal plane and one oxygen atom [2.259(3) A] from a bis-monodentate tp group at the axial position. In the discrete dinuclear [Ni2(tp)(pren)4(Him)2]2+ cation of complex (2), each NiII center is coordinated by five nitrogen atoms [Ni—N 2.069(3)–2.109(2) A] from one Him group and two pren groups, and completed by one oxygen atom [Ni—O 2.138(3) A] from a bis-monodentate tp group to furnish a distorted octahedron. Magnetic susceptibility studies show that the pair of metal atoms, although being separated by >11.5 A, exhibit weak intramolecular antiferromagnetic interactions in complexes (1) (g = 2.07 and J = −3.4 cm−1) and (2) (g = 2.10 and J = −0.7 cm−1). The electrochemical behaviors of the complexes have also been studied by cyclic voltammogram processes.