Three CdII coordination polymers (CPs), named as {[Cd2(DDPP)(DMF)(H2O)]·DMF}n (1), {[Cd2(DDPP)(H2O)2]·DMA·H2O}n (2), [Cd(H2DDPP)]n (3), based on 3,5‐di(2′,5‐dicarboxylphenyl)pyridine) (H4DDPP), were synthesized under solvothermal methods. Structural analysis indicates that the H4DDPP ligand of 1–3 adopt (κ1‐κ1)‐(κ1‐κ1)‐(κ1‐κ2)‐(κ1‐κ1)‐μ8, (κ1‐κ1)‐(κ1‐κ2)‐(κ1‐κ2)‐(κ1‐κ1)‐μ10, and (κ0‐κ0)‐(κ1‐κ2)‐(κ1‐κ2)‐(κ0‐κ0)‐μ6 coordination modes, respectively. CP 1 is a 2‐nodal (4,8)‐c alb‐4,8‐Pbcn network. CP 2 is a 3D 4,8‐c flu/fluorite network. CP 3 displays a 2D layer, which is further connected with hycrogen‐bonding interactions between layers to form supramolecular framework. Moreover, the fluorescent features of 1–3 were studied in aqueous systems and the values of detection limit (DL) are also calculated by 3σ/ksv. The results reveal that 1–3 have good ability on probing CrVI/FeIII ions.