Three couples of coordination polymers (CPs), namely, [Co((R/S)-Hcna)₂]_n (1-D/L), [Cd₆((1R,2R/1S,2S)-cpba)₄(phen)₆(H₂O)₃]_n (2-D/L) and [Cd₂((1R,2R/1S,2S)-Hcpba)₂(phen)₂]_n (3-D/L) {(R/S)-H₂cna = (R/S)-6-(1-carboxyethoxy)-2-naphthoic acid, (1R,2R/1S,2S)-H₃cpba = (1R,2R/1S,2S)-2,2′-((5-carboxy-1,3-phenylene)bis(oxy))dipropionic acid, phen = 1,10-phenanthroline} are successfully synthesized under hydrothermal conditions. Structural analysis shows that CP 1 has a 3D 3,6-c net structure with a point symbol of (4·6²)₂(4²·6¹⁰·8³). CPs 2 and 3 are obtained under very similar reaction conditions except using different solvent ratios. The presence of the planar chelating ligand phen in CPs 2 and 3 limited the spatial growth of the structure, resulting in the formation of different 1D structures. All CPs crystallized in the chiral space group P2₁, CPs 1–3 are all SHG active. Their luminescence sensing activities for organics such as antibiotics, pesticides and nitro aromatics are also investigated. The results showed that CP 1 can effectively identify trace amounts of nitrofurans (NFs) and CP 3 has obvious recognition ability toward nitrofurans (NFs) and nitroimidazoles (NMs). Both CPs 1 and 3 could selectively detect 2,6-dichloro-4-nitroaniline (DCN). The luminescence of CPs 1 and 3 can also be quenched by (D/L)-4-nitrophenylalanine ((D/L)-NPA) and (1R,2R/1S,2S)-2-amino-1-(4-nitrophenyl)propane-1,3-diol ((1R,2R/1S,2S)-ANPO).