Two new Cu(II)-organic polymers supported by different N-heterocyclic ligands, namely {[Cu(btx)(2)]center dot Cl-2}(n) 1 (btx=1,4-bis(triazol-1-ylmethyl)-benzene) and {[Cu(bbbm)(Ac)(2)]center dot(CH3OH)(2)}(n) 2 (bbbm=1,1'-(1,4-butanediyl)bis-1H-benzimidazole) are designed and synthesized in order to ascertain the influence of coordination polymeric structure on catalytic activity. Single-crystal X-ray diffraction shows that 1 assumes a 2D cationic rhombohedral grid network arrangement, whereas 2 features a 1D zigzag chain structural motif in which Cu atoms are bridged by mu(2)-bbbm ligands. Both of them reveal impressive catalytic capability for the selectively oxidative coupling of 2,6-di-t-butylphenol to the corresponding diphenocluinone in excellent yield using H2O2 as oxidant and KOH as co-catalyst in water and allow reuse without a significant loss of activity through three runs with the hindered phenol. Under the similar reaction conditions, the two polymers also accelerate the selectively coupling of 2,4-di-tbutylphenol to generate the relevant biphenol with moderate to high efficiencies. The transformation of 2,6-dimethylphenol mediated by polymers 1 and 2 proceeds smoothly with 100% and 94.5% conversion, respectively. It is found that polymer I offers the superior results in terms of reactivity and selectivity to 2 for such processes, indicating the crucial role of structural parameters in catalytic performance of polymers. Furthermore, the ability of 1 and 2 to undergo homogeneous oxidation couplings of these substituted phenols in 1.5:1 (v/v) methanol-toluene mixture is explored as well to demonstrate the advantages of heterogeneous catalysis. (C) 2008 Elsevier B.V. All rights reserved.