Under solvothermal condition, one new three-dimensional Co(II) metal–organic framework (MOF), namely {[Co2(TFBA)(μ3-O)(dpa)]·3DMF·9H2O}nCoMOF-1 (H3TFBA = tris(3′-F-4′-carboxybiphenyl)amine, dpa = 9,10-di(4-pyridyl)anthracene, DMF = N,N-dimethyl formamide) was successfully synthesized and characterized. CoMOF-1 displays three-dimensional framework with 2, 3, 10-c network topology based on tetranuclear [Co4O14] units. Besides, magnetic properties revealed that antiferromagnetic interactions between two adjacent metal centers. In addition, a series of luminescence sensing investigations demonstrated that CoMOF-1 could be used as a sensitive material toward nitrofuran antibiotics (nitrofurazone, NFZ, nitrofurantoin, NFT, furazolidone, FZD) with the average quenching Ksv values of 1.84 × 105 M−1, 1.78 × 105 M−1, and 1.2 × 105 M−1, and the limit of detection of 0.14 μM, 0.15 μM and 0.23 μM, respectively. Additionally, the possible luminescent quenching reasons for nitrofuran antibiotics were mainly due to competitive excitation and electron transfer mechanism. [ABSTRACT FROM AUTHOR]