Organic semiconductors have witnessed a prolific boom for their potential in the manufacturing of lightweight, flexible, and even biocompatible electronics. One of the fields of research that has yet to benefit from organic semiconductors is high temperature electronics. The lightweight nature and robust processability is attractive for applications such as aerospace engineering, which require high temperature stability, but little has been reported on taking such a leap because charge transport is temperature dependent and commonly unstable at elevated temperatures in organics. Historically, mechanistic studies have been bound to low temperature regimes where structural disorders are minimal in most materials. Discussed here is a blending approach to render semiconducting polymer thin films thermally stable in unprecedented operation temperature ranges for organic materials. We found that by utilizing highly rigid host materials, semiconducting polymer domains could be confined, thus improving their molecular and microstructural ordering, and a thermally stable charge transport could be realized up to 220°C. With this blending approach, all-plastic high temperature electronics that are extremely stable could also be demonstrated. In efforts to establish a universal route towards forming thermally stable semiconducting blends, we found that the molecular weight of conjugated polymer plays a crucial role on the miscibility of the blends. Finally, we found that the choice of the host matrix ought to consider the charge trapping nature of the insulator.<br>