We present a thermally stable, mechanically compliant, and sensitive polymer-based NO2 gas sensor design. Interconnected nanoscale morphology driven from spinodal decomposition between conjugated polymers tethered with polar side chains and thermally stable matrix polymers offers judicious design of NO2-sensitive and thermally tolerant thin films. The resulting chemiresitive sensors exhibit stable NO2 sensing even at 170 °C over 6 h. Controlling the density of polar side chains along conjugated polymer backbone enables optimal design for coupling high NO2 sensitivity, selectivity, and thermal stability of polymer sensors. Lastly, thermally stable films are used to implement chemiresistive sensors onto flexible and heat-resistant substrates and demonstrate a reliable gas sensing response even after 500 bending cycles at 170 °C. Such unprecedented sensor performance as well as environmental stability are promising for real-time monitoring of gas emission from vehicles and industrial chemical processes.