Five novel coordination polymers based on the 2,6-pyridinedicarboxylic acid (H2pdca), namely [Co(pdca)(bibp)0.5H2O)2]n (1), [Ni(pdca)(bibp)0.5(H2O)2]n (2), [Co(pdca)(bbibp)1.5]n (3), [Ni(pdca)(bbibp)1.5]n (4) and Zn(pdca)(bbibp)0.5]n (5) (bibp = 4,4′-bis(imidazole) biphenyl, bbibp = 4,4′-bis(benzoimidazo-l-yl)biphenyl and DMF = N, N’dimethylformamide) have been synthesized under solvothermal conditions. Single crystal X-ray diffraction analysis reveals that all the complexes have 3D framework structures. In addition, the properties of the complexes for photo-catalytic degradation of organic dyes were discussed. Moreover, luminescence studies reveal that complex 5 shows strong luminescent property and could be a fluorescence sensor for the detection of Cr2O72−ion and antibiotics chloramphenicol. The Ksv values of 5 for Cr2O72− ion and chloramphenicol are 8.05 × 103 M−1 and 6.69 × 103 M−1, respectively. Meanwhile, the possible mechanism for the luminescence quenching of 5 has been discussed.