Novel solid copper(II) complexes were obtained from the polyampholyte poly(EGDE-MAA-IM) and the polyelectrolyte poly(EGDE-MAA) polymers with copper salts at different concentration levels. The materials were characterized employing solid-state Nuclear Magnetic Resonance (NMR), Fourier Transform infrared (FTIR), X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC) and thermogravimetry (TG). The reticulation induced by MAA in these materials against the poly(EGDE-IM) gel was analyzed by DSC. The coordination behavior of the carboxylic acid of MAA, compared to that provided by the imidazole ring, was studied through solid-state 13C NMR and changes in the FTIR spectra. The non-homogenous character of the doped and undoped materials was analyzed by the glass transition temperature (Tg), 2D 1H-13C WISE NMR and proton spin-lattice relaxation time in the rotating frame (TH 1ρ). In particular, the TH 1ρ and TH 1 values in the complexes decreased with the Cu(II) concentration, showing the high sensitivity of both parameters to the presence of a paramagnetic ion. Finally, the thermogravimetric studies indicated that the presence of the imidazole ring was decisive for the stability of the Cu(II) complexes and for the undoped polymers. © 2008 Elsevier Ltd. All rights reserved.