By introducing different metal ions, six new coordination polymers (CPs) [Zn(L)0.5(DTSA)]·H2O (CP1), [Cd(L)0.5(DTSA)(H2O)] (CP2), [Mn(L)0.5(DTSA)(H2O)] (CP3), [Co(L)0.5(DTSA)(H2O)] (CP4), [Ni(L)0.5(DTSA)(H2O)] (CP5), [Pb2(L)0.5(DTSA)2] (CP6), [N,N′-bis(4-methylenepyridin-4-yl)-1,4-benzenedicarboxamide (L), 2,2′-dithiodibenzoic acid (H2DTSA)] have been synthesized under hydrothermal conditions. CP1 is a unified node (4,4)-connected network derived from Zn2 nodes, pairs of DTSA anions and μ2-L linkers. CP2–CP5 display similar binode (4,4)-connected layers based on single metal centers, μ2-DTSA anions and μ4-L linkers. CP6 show a novel 3D (3,4,4,5)-connected Pb-based framework, which is constructed form Pb-DTSA layers and μ4-L linkers. The effect of metal ions on the architectures of the title complexes is investigated. The experimental results indicate that CP1, CP2 and CP6 are efficient luminescent sensors for the detection of Fe3+ ions (CP1 and CP2) and dimethyl sulfoxide (DMSO) (CP1 and CP6). In addition, CP3–CP5 show different electrochemical response to nitrite and bromate in water solution.