Three Cd(II) coordination polymers (CPs), {[Cd(TCPA)(L)]·H2O}n (1), {[Cd(1,2-BDC)(L)]·H2O}n (2) and [Cd2(1,3-BDC)2(L)(H2O)2]n (3) (H2TCPA = 2,3,5,6-tetrachloroterephthalic acid, 1,2-H2BDC = 1,2-benzenedicarboxylic acid and 1,3-H2BDC = 1,3-benzenedicarboxylic acid, L = 1,3-bis(5,6-dimethylbenzimidazol-1-yl)propane) were hydrothermally synthesized and characterized. 1 features a 2D {44} structure, which constructs a 3D supramolecular structure through π-π stacking interactions. 2 shows a 1D ladder-like chain which is additional extended into a 3D supramolecular network via π-π stacking interactions. 3 retains a 2D (3,4)-connected 3,4L83 net which can be broadened into a 3D supramolecular framework by OH···O hydrogen bonds. Both 1, 2 and 3 could serve as efficient probes for detecting of Cr2O72– anions with high quenching efficiency (Ksv) values (7820 M−1, 9460 M−1 and 20018 M−1 for 1, 2 and 3, separately) and low detection limit (0.42 μM, 0.37 μM and 0.15 μM for 1, 2 and 3, respectively).