An organic ion-pair comonomer (IPC) based on anionic and cationic styrenic monomers was synthesized and copolymerized with n-butyl acrylate (BA) by reversible addition fragmentation chain transfer (RAFT) polymerization to generate physically cross-linked polyampholyte ionomer networks. Evidence of microphase separation of the ion pairs to produce ion-rich domains was found by rheological and atomic force microscopy measurements. Comparison of these polymers to chemically similar cationic and anionic ionomers with only one type of ion covalently bound to the polymer backbone demonstrated that the connectivity of the ions to the polymer backbone had a strong effect on the viscoelastic properties. Characterization of the corresponding polyelectrolytes showed a ca. 125 degrees C increase in the glass transition temperature (T-g) from the cationic to the polyampholytic polyelectrolyte. In the ionomers, this elevated T-g allowed the vitrification of the ion-rich domains at ambient temperatures in the polyampholyte networks over a range of ion-pair concentrations. This produces long-lived physical cross-links at room temperature. The weak microphase separation of the neutral and ionic segments resulted in the increase of the effective volume fraction of the ion-rich domains, increasing the resulting modulus of the ionomers and plasticization of the ion-rich domains with the low T-g BA segments. This plasticization allowed ion hopping at accessible temperatures to enable thermoplasticprocessing at 150-200 degrees C. More generally, this work demonstrates that variation of the connectivity of the ion pairs is a facile method to tune the thermomechanical behavior of ionomers with nonmetal ion pairs.