Solvothermal reactions of a tetradentate imidazole-containing ligand, 3,3′,5,5′-tetra(1H-imidazol-1-yl)-1,1′-biphenyl (L), combined with Zn(II) salt in the presence of varied auxiliary dicarboxylic acids yield three new polymers with (4,4) topologies, [Zn2(L)(o-BDC)2] (1), [Zn2(L)(m-BDC)2]·4H2O (2), [Zn2(L)(p-BDC)2]·2MeOH·4H2O (3) (o-H2BDC = phthalic acid, m-H2BDC = isophthalic acid, p-H2BDC = terephthalic acid). Single crystal X-ray diffraction analysis has revealed that complexes 1 and 2 consist of two-dimensional (2D) layers with different macrocycles, 40- and 52-membered macrocycles in 1, while one 46-membered macrocycles in 2, which is further connected by carboxylates to bring about three-dimensional (3D) frameworks. In complex 3, the layers formed by L, partial p-BDC2− and Zn(II), are pillared by the rest p-BDC2− to result in the final 3D structure. Furthermore, the photoluminescence of these compounds as well as the sorption properties of 2 were investigated.