The effect of temperature on the structure and single chain conformation of associating solutions of carboxy-telechelic polystyrene ionomers has been investigated in the dilute to semidilute concentration regime using the technique of small-angle neutron scattering. By applying different labeling methods, the temperature dependence of both the total scattering and single chain scattering functions was obtained independently. It was observed that temperature has a significant impact on the structure of the ionomer aggregates. Increasing temperature results in dissociation of the aggregated particles and the formation of smaller size multimers. Interestingly, the extent to which the multimers dissociate at a specific temperature compared to their initial state at room temperature is independent of concentration or ionic level, which indicates that it is independent of the degree of aggregation of particles. This leads to the conclusion that the apparent degree of aggregation can be controlled independently by concentration and temperature. For all systems studied the multimers formed through the ionic association keep an extended configuration over all the temperatures investigated. The Flory-Huggins polymer-solvent interaction parameter of the ionomer solutions showed only a slight decrease with increasing: temperature. Despite the significant effect of temperature on the multimer structure, temperature was not observed to influence the single chain dimensions of the ionomer solutions. It was observed that the single chain dimensions remained unchanged over the range of variables studied. On the basis of these results, it is proposed that dissociation of the multimers takes place by disruption of the configuration of only a small number of bridging chains which connect different ionic clusters without influencing the main architecture of the associating structure.