Four lanthanide coordination polymers were constructed from mixed ligands of phenanthroline derivative and flexible polydentate ligands, [Gd 2 (1,3-BDC) 3 (MOPIP) 2 ] n •nH 2 O (1), [Gd(1,4-BDC) 1.5 (MOPIP)] n (2), [Yb(1,4-BDC) 1.5 (MOPIP)] n (3) and [Sm(1,4-BDC) 1.5 (MOPIP)] n (4), (MOPIP = 2-(4-methoxyphenyl)-1Himidazo[4,5-f ][1,10]phenanthroline, 1,3-BDC = benzene-1,3-dicarboxylic acid, 1,4-BDC = benzene-1, 4-dicarboxylic acid). The polymers have been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction analysis. Compound 1 possesses one-dimensional chain structure, and expands into the three-dimensional supramolecular architecture by π • • • π stacking and hydrogen-bonding interactions. Meanwhile, compounds 2-4 exhibit three-dimensional frameworks with pcu topology (4 12 •6 3). The structural differences among such compounds show that the steric hindrances of benzene dicarboxylic acid ligands play a key role in the assembly and the structures of the title compounds. Compounds 1 and 2 act as efficient Lewis acid catalysts for the cyanosilylation of benzaldehyde in high yields, due to the strong Lewis acidity.