Furthermore, the enhanced stability of these compounds against photooxidation, compared to acenes, underscores their potential for practical applications. We validated this potential by integrating them into organic field-effect transistor (OFET) devices, where they exhibited ambipolar semiconducting behavior with good hole and electron mobilities-ultimately showcasing the utility of our design approach. Overall, our findings establish indoloindolizines as a promising platform for the development of stable, tunable organic materials. By employing the Glidewell-Lloyd rule as a foundational guideline, we have advanced the field of organic optoelectronics and opened new opportunities for device applications through rational molecular design.