Three new mixed-ligand metal-organic frameworks based on 5,5′-(butane-1,4- diyl)-bis(oxy)-diisophthalic acid and transitional metal cations with the help of two ancillary bridging N-donor pyridyl and imidazole linkers, [Zn(L)0.5(4,4′-bpy)]·2(H2O) (1), [M(L)0.5(bib)]·4(H2O) (M = Zn (2), Co (3)), (4,4′-bpy=4,4′–bipyridine, bib=1,4-bis (1H-imidazol-1-yl)-butane), have been synthesized under solvothermal conditions. Their structures and properties were determined by single-crystal and powder X-ray diffraction analyses, IR spectra, elemental analyses and thermogravimetric analyses (TGA). Compounds 1–3 display a 3D 3-fold interpenetrated frameworks linked by the L4− ligands, ancillary N-donor linkers and the free water molecules in the crystal lattice. Topological analysis reveals that 1–3 are a (4,4)-connected bbf topology net with the (64·82)(66) topology. The effects of the L4− anions, the N-donor ligands, and the metal ions on the structures of the coordination polymers have been discussed. Furthermore, luminescence properties and thermogravimetric properties of these compounds were investigated.