Copper(II) complexation of amino functions supported on triethyleneglycol dimethacrylate-crosslinked polyacrylamides in varying structural environments was investigated. The electron parametic resonance spectrum is used to probe the coordination structure and the nature of the Cu-N bond of the derived aminopolyacrylamide-Cu(II) complexes. The extent of the hydrophilic and flexible crosslinking agent in the macromolecular matrix has a significant effect on the coordination structure of the complexes.