Utilizing the flexible carboxylic acid ligand, tri(4‐carboxybenzyl) amine (H3L), three new coordination polymers Na[Cd(L)]n·3nH2O (1), [Cd(HL)(4,4’‐bipy)0.5(H2O)]n (2) (4,4’‐bipy = 4,4’‐bipyridine) and [Cd(HL)(2,2’‐bipy)]n (3) (2,2’‐bipy = 2,2’‐bipyridine) have been successfully synthesized. Compounds 1 and 2 are all 2D structures with (3,6) 2‐nodal as kgd topology, while compound 3 is a 1D chain structure. The powder X‐ray diffraction and the thermal stabilities were studied for 1‐3. In addition, the solid‐state luminescence properties of compounds 1‐3 were also tested at room temperature, indicating their application prospects in fluorescent materials.