Neutralization of carboxyl-terminated polybutadienes with tri-or tetravalent metal was carried out with different ratios of the corresponding neutralizing agents. The network structures of the prepared materials were investigated through their molecular, thermal, dynamic mechanical, and dielectric properties. The nature, the density, and the efficiency of the ionic interactions influence the solubility, the formation, and the thermal stability of the three-dimensional cross-linked ion-containing polymers.