The network structure and chain dynamics of ionic elastomers based on carboxylated nitrite rubber (XNBR) cross-linked with different content of magnesium oxide (MgO) have been studied by different low-field time-domain NAIR experiments. Ionic contacts created during the vulcanization tend to aggregate trapping some polymer segments that show restricted mobility as it was quantified by analyses of refocused free induction decays. Increasing the MgO content above the stoichiometric fraction has no effect on the amount of trapped polymer segments, but it increases the network cross-link density as measured by multiple-quantum (MQ) NMR experiments. The central finding of this work is that MgO addition above the stoichiometric content enhances the mechanical properties by creating a larger number of smaller ionic clusters, which act as dynamic cross-links, but are not readily seen by other techniques. Changes in the network structure and morphology of segregated thermolabile ionic domains have an impact on the ionic rearrangement dynamics and, in consequence, on the thermoplastic behavior of these materials at elevated temperatures.