Dynamic supramolecular networks are constantly accompanied by thermal instability. The fundamental reason is most reversible noncovalent bonds quickly decay at elevated temperatures and dissociate below 100 °C. Here, in this paper, we realize a reversible ion-dipole interaction with high-temperature stability exceeding 150 °C. The resultant supramolecular network can simultaneously possess mechanical strength of 1.32 MPa (14.8 times that of pristine material), dynamic self-healing capability, and a stable working temperature of up to 200 °C. From the prolonged characteristic relaxation time of 600 s even at 100 °C, our material represents one of the most thermally stable dynamic supramolecular polymers. These remarkable performances are achieved by using a new multivalent yet low-entropy-penalty molecular design. In this way, the noncovalent bond can reach a high enthalpy while minimizing the entropy-dominated thermal dissociations.