The overused of nitroaromatic explosives and antibiotics had led to severe environment and health issues. The detection on nitroaromatic explosives and antibiotics with high selective and sensitive is pressing need. Herein, a new cadmium-based metal–organic framework (MOF), namely {[(CH3)2NH2]2[Cd3(TCPPDA)2]·5DMF·8H2O}n MOF-1 (H4TCPPDA = N,N,N’,N’-Tetrakis(4-carboxyphenyl)-1,4-phenylenediamine) had been successfully synthesized and characterized. Single crystal X-ray diffraction analysis displayed that MOF-1 possesses 3D (4,8)-connected framework with the Schläfli symbol of {42.6}2{44.62.87.102} comprising trinuclear [Cd3(COO)8] SBUs. The detection ability of MOF-1 toward nitroaromatic explosives and antibiotics were evaluated. Notably, MOF-1 had high selectivity and sensitivity for 4-Nitrophenol (4-NP) and nitrofuran antibiotics (nitrofurazone, NFZ, nitrofurantoin, NFT) with low detection limits of 7.5, 1.39 and 1.23 μM. Furthermore, the possible quenching mechanisms were also explored by calculations and experiments.