The inherent benefits of C−H activation have given rise to innovative approaches in designing organic optoelectronic molecules that depart from conventional methods. While theoretical calculations have suggested the suitability of the 2,6-naphthyridine scaffold for electron transport materials (ETMs) in organic lightemitting diodes (OLEDs), the existing synthetic methodologies have proven to be insufficient for the construction of multiple arylated and fully aryl-substituted molecules. Herein, we present a solution for the synthesis of 2,6-naphthyridine derivatives, with the rhodium-catalyzed consecutive C−H activation−annulation process of fumaric acid with alkynes standing as the pivotal step within this strategy. The ETMs, purposefully designed and synthesized based on the 2,6-naphthyridine framework, exhibit an impressively high glass-transition temperature (T g ) of 282 °C and high electron mobility (μ e ), setting a new benchmark for ETMs in OLEDs with a μ e exceeding 10 −2 cm 2 V −1 s −1 . These materials prove to be versatile ETM candidates suitable for red, green, and blue phosphorescent OLED devices.