By employing a tris(4-(1H-imidazol-1-yl)phenyl)amine (Tipa) ligand, three new metal organic frameworks, [Zn-2(Tipa) (4,4'-bpdc)(1.5)(H2O)(NO3)]center dot 2(DMF)center dot H2O (1; 4,4'-bpdc = 4,4'-biphenyldicarboxylate, DMF = N,N-dimenthylformamide), [Cd(Tipa)Cl-2]center dot 2(DMF)center dot H2O (2), and [Co(Tipa)Cl-2(H2O)]center dot DMF center dot H2O (3), have been synthesized solvothermally. Compound 1 features a three-dimensional (3D) pillared-layer structure with low band gap and interesting photocatalytic properties. Compound 2 is a 2-fold interpenetrating (3,6)-connected porous framework, and it shows highly selective adsorption of C2H2, CO, and C2H4 over CH4. Compound 3 with honeycomb-like layers exhibits unusual 2D + 2D -> 3D polycatenation (2D = two-dimensional). The luminescent properties for these compounds were also investigated.