Reliability remains an ongoing challenge for organic light emitting diodes (OLEDs) as they expand in the marketplace. The ability to withstand operation and storage at elevated temperature is particularly important in this context, not only because of the inverse dependence of OLED lifetime on temperature, but also because high thermal stability is fundamentally important for high power/brightness operation as well as applications such as automotive lighting, where interior car temperatures often exceed the ambient by 50 °C or more. Here, we present a strategy to significantly increase the thermal stability of small molecule OLEDs by co-depositing an amorphous fluoropolymer, Teflon AF, to prevent catastrophic failure at elevated temperatures. Using this approach, we demonstrate that the thermal breakdown limit of common hole transport materials can be increased from typical temperatures of â1/4100 °C to more than 200 °C while simultaneously improving their electrical transport properties. Similar thermal stability enhancements are demonstrated in simple bilayer OLEDs. These results point toward a general approach to engineer morphologically-stable organic electronic devices that are capable of operating or being stored in extreme thermal environments.