Pollutants caused by heavy metals and nitroaromatics (NACs) have become a serious environmental issue. Herein, we designed and synthesized series of coordination polymers (CPs) as a universal sensing platform that demonstrated a great potential for detecting and removing heavy metals and NACs. The results showed the different structural motifs can be controlled by N-donor ligands. Without using bridging N-containing ligand, five non-interpenetrating 1D chain (1 and 7) and 2D layer (4–6) were constructed. In the presence of 4,4′-bipy ligand, two 3D 4-fold interpenetrated frameworks with pcu topology and fsg topology for 2 and 3 were produced, respectively. 1,2,4,5 not only display sensitivity for nitroaromatics (NACs) and small organic solvents, but also have impressive removal capabilities of Cu2+ ion. Sensing studies of samples to detect nitro-aromatic compounds reveal highly detection of 2,4,6-Trinitrophenol (TNP) with a low limit of detection (LOD: 1.16 ppm for 1, 2.59 ppm for 2, 3.36 ppm for 4 and 2.30 ppm for 5). The coefficient of correlations between (I0–I)/I0 and the content of Cu2+ ions was got in the detection limit range of 1.04–2.57 ppm for 1, 2, 4, 5. The immobilized CuII ions could be easily removed by EDTA without structural decomposition.