Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are of paramount importance in the quest for organic optoelectronic materials. Among these methods, transition-metal-catalyzed oxidative Ar-H/Ar-H coupling reactions between two (hetero)arenes have emerged as a concise and effective approach for generating a wide array of bi(hetero)aryl and fused heteroaryl structures. This innovative approach bypasses challenges associated with substrate pre-activation processes, thereby allowing for the creation of frameworks that were previously beyond reach using conventional Ar-X/Ar-M coupling reactions. These inherent advantages have ushered in new design patterns for organic optoelectronic molecules that deviate from traditional methods. This ground-breaking approach enables the transcendence of the limitations of repetitive material structures, ultimately leading to the discovery of novel high-performance materials. In this Perspective, we provide an overview of recent advances in the development of organic optoelectronic materials through the utilization of transition-metal-catalyzed oxidative Ar-H/Ar-H coupling reactions. We introduce several notable synthetic strategies in this domain, covering both directed and non-directed oxidative Ar-H/Ar-H coupling strategies, dual chelation-assisted strategy and directed ortho-C-H arylation/cyclization strategy. Additionally, we shed light on the role of oxidative Ar-H/Ar-H coupling reactions in the advancement of high-performance organic optoelectronic materials. Finally, we discuss the current limitations of existing protocols and offer insights into the future prospects for this field.