Two novel coordination polymers with double-layer structures were constructed from a tripodal ligand TCMB (1,3,5-tris(carboxymethoxy) benzene) by controlling the solvent and diffusion velocity of the reaction systems. Both solvated isomers [Cu-3(TCMB)(2)(C5H5N)(3)(H2O)(3) center dot 10H(2)O] (1, P6/m, a = b = 16.753( 1), c = 10.811( 1) angstrom, alpha = beta = 90.00 degrees, gamma = 120.00 degrees) and [Cu-3(TCMB)(2)(C5H5N)(3)(H2O)(3) center dot 7.66H(2)O center dot DMF] (2. P-3, a = b = 28.937( 3), c = 10.694( 1) angstrom, alpha = beta = 90.00 degrees, gamma = 120.00 degrees) exhibit peculiar metal disordering with fixed ligands due to the fact that the ligand can provide excessive potential coordinative sites with deficient metal centers available. Supramolecular isomerism induced by metal disordering was found for the first time.