There has been extensive interest in the construction of grid-type supramolecular complexes because of their important roles in material science. However, only few of these compounds have been explored for selective adsorption of dyes. Two novel grid-type architectures composed of mixed valence copper ions and polynitrogen heterocyclic ligands have been successfully synthesized. Interestingly, one of the grid-type architectures with modest grid size could efficiently and selectively adsorb dye molecules.