In this work, we designed and presented three Co(II) metal-organic frameworks (MOFs), {[Co3(NTB)2(DIMB)]·H2O·DMA}n (NTB-1), {[Co3(NTB)2(DMIMB)]·DMA}n (NTB-2), and {Co(HNTB)(dpa)(H2O)2}n (NTB-3) (H3NTB = 4, 4′, 4′’-nitrilotrisbenzoic acid, DIMB = 1,4-di(1H-imidazol-1-yl) butane), DMIMB = 1,4-di(1H-2-methylimidazol-1-yl) butane), dpa = 9,10-di(4-pyridyl)anthracene) by mix-ligand strategy. X-ray diffraction analysis revealed that NTB-1 and NTB-2 exhibited three-dimensional (3D) architectures with 2, 3, 8-c net topology based on the trinuclear [Co3O12] units, while NTB-3 displayed 2D framework and further subsequently extended to 3D supramolecular structure via classical OH···O hydrogen bond. Thermogravimetric analysis (TGA) and Powder X-ray diffraction (PXRD) exhibited thermal and chemical stability of NTB-1–3. Investigation of magnetic susceptibilities indicated the antiferromagnetic coupling was existed in neighboring Co(II) ions for NTB-1–3. NTB-3 displayed single-molecule magnet characteristics with τ0 = 1.67×10−5 s and Ueff = 9.4 K. Luminescence sensing analyses demonstrated that NTB-1–3 can be regarded as promising luminescent sensors for Pb2+, Fe3+, CrO42− and Cr2O72−. Finally, the possible quenching mechanism for various ions were fully discussed.