The chemiluminescence of a luminol-H(2)O(2) system is found to be remarkably enhanced by the Ce(IV) complexes of EDTA-bridged cyclodextrin dimers. The dimers were proved to work much more efficiently than the corresponding monomer. The cavity shape of cyclodextrin moieties and their cooperation displayed an important role in amplifying the chemiluminescence. Further modification of either the cyclodextrin rims or the EDTA linker altered significantly the catalytic abilities of the cyclodextrin dimers, and the examination of the effect of substituents on the chemiluminescence outputs suggested that the proximity between the cyclodextrin cavity and the metallic center might account for the amelioration of the chemiluminescence output.