AbstractThree coordination polymers, namely {[Cu(5‐nipa)(L22)](H2O)2}n (1), [Zn(5‐nipa)(L22)(H2O)]n (2), and {[Cd2(5‐nipa)2(L22)(H2O)3](H2O)3.6}n (3), were prepared under similar synthetic method based on 1,2‐(2‐pyridyl)‐1,2,4‐triazole (L22) and ancillary ligand 5‐nitro‐isophthalic acid (5‐H2nipa) with CuII, ZnII, and CdII perchlorate, respectively. All the complexes were characterized by IR spectroscopy, elemental analysis, and powder X‐ray diffraction (PXRD) patterns. Single‐crystal X‐ray diffraction indicates that complexes 1 and 2 show similar 1D chain structures, whereas complex 3 exhibits the 2D coordination network with hcb topology. The central metal atoms show distinct coordination arrangements ranging from distorted square‐pyramid for CuII in 1, octahedron for ZnII in 2, to pentagonal‐bipyramid for CdII in 3. The L22 ligand adopts the same (η3,μ2) coordination fashion in complexes 1–3, while the carboxyl groups of co‐ligand 5‐nipa2– adopt monodentate fashion in 1 and 2 and bidentate chelating mode in 3. These results indicate that the choice of metal ions exerts a significant influence on governing the target complexes. Furthermore, thermal stabilities of complexes 1–3 and photoluminescent properties of 2 and 3 were also studied in the solid state.