Complexes of amine-terminated telechelic polybutadiene (ATPB) with Cu2+ and Zn2+ were studied by ESR and DSC. The effect of annealing, presence of oxygen, and Zn2+ content on the thermal transitions and Cu2+ complexation have been investigated. This study has indicated that Zn2+ is not only a diamagnetic diluent but can also significantly affect the ionic distribution, the degree of ionic clustering, and the appearance of the glass transition. The ESR signal from the cupric ion disappears on annealing to 523 K and reappears at ambient temperature only when ATPB/Cu2+ is exposed to oxygen. Zn2+ accelerates the rate of disappearance of the Cu2+ Signal for annealing in air or in vacuo. These results have been explained by a mechanism based on the formation of allyl radicals on annealing, reaction of these radicals with Cu2+, reduction of Cu2+ to, Cu2+, and reoxidation to Cu2+. Formation of allyl radicals is enhanced by Zn2+. The glass transition of ATPB measured by DSC (heating rate 20 K/min) is not affected by the presence of Cu2+ or Zn2+; the transition in ATPB/Cu2+ (chi(Cu) = 0.02) is weaker in the presence of Zn2+ and is not detected for chi(Zn) greater than or equal to 1.98. An exothermic transition around 360 K accompanies the changes in the glass transition region induced by Zn2+; the corresponding Q(exo) (J/g) is enhanced in ATPB containing both cations, compared to ATPB containing Cu2+ only. This transition, which is absent in ATPB/Zn2+ (no copper), is assigned to the formation of ionic domains. Swelling experiments and T-g measurements at heating rates lower than 20 K/min indicate the formation of a reversibly cross-linked network in ATPB containing Cu2+ and Zn2+. We explained these results based on the combined effects of the two cations : Zn2+ cations provide the cross-links by acting as Lewis acids, and Cu2+ cations connect the end groups by complexation of the piperazine groups.