A series of new metal–organic frameworks (MOFs), namely, [Co2(L)(H2O)3]·5H2O (1), [Co(L)0.5(biim-4)]·H2O (2), [Co(L)0.5(biim-5)]·H2O (3), [Co(L)0.5(biim-6)]·1.5H2O (4), [Co2(L)(BIE)1.5]·H2O (5), [Co2(L)(bbip)2]·3H2O (6), [Ni(L)0.5(biim-4)1.5] (7), [Ni2(L)(biim-6)2]·2H2O (8), [Zn(L)0.5(biim-4)]·H2O (9), [Zn(L)0.5(biim-5)]·H2O (10), [Zn(L)0.5(biim-6)]·H2O (11), [Zn2(L)(BIE)] (12), and [Zn(L)0.5(bbip)0.5]·0.5H2O (13), where biim-4 = 1,1′-(1,4-butanediyl)bis(imidazole), biim-5 = 1,1′-(1,5-pentanedidyl)bis(imidazole), biim-6 = 1,1′-(1,6-hexanedidyl)bis(imidazole), BIE = 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-imidazole), bbip = 1,1′-(1,4-butanediyl)bis(imidazole-2-phenyl), and H4L = 5,5′-(ethane-1,2-diyl)-bis(oxy)diisophthalic acid, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD) and thermogravimetric (TG) analyses. Compound 1 features a 3D 2-fold interpenetrating diamond framework. Compounds 2–4 and 9–11 are isostructural and display 3D 3-fold interpenetrating frameworks with (64·82)(66) topologies. Compound 5 exhibits a 3D (4,6)-connected (64·72)(4·65)(42·64·75·84) topology. Compounds 6 and 7 are 3D 2-fold interpenetrating frameworks with (66)2(64·82) and (42·64)(43·67) topologies, respectively. Compound 8 shows a 2D double-layer structure. Compound 12 possesses a 3D framework with (4,6)-connected (3·42·52·6)(32·42·52·64·74·8)2 topology. Compound 13 has a 3D 2-fold interpenetrating framework with (44·62)(44·610·8) topology. The luminescent properties of 9–13 have also been investigated in detail.