The synthesis of fused heteroaromatics is an important research area in organic chemistry and it has significant implications on the investigations of organic optoelectronic materials and devices. C—H bond is one of the most ubiquitous chemical bonds in organic compounds. The direct construction of fused heteroaromatics via the C—H bond cleavage and direct functionalization features concision and high efficiency, which could solve the limitations on the substrate preparation and product structural diversity in conventional synthetic methods. In this account, we review our works on the construction of fused heteroaromatics based on chelation-assisted transition metal-catalyzed oxidative C—H/C—H cross-coupling between(hetero)arenes/intramolecular cyclization during the past six years, including a comprehensive discussion of the features, advantages and reaction mechanisms of these reactions, and the applications of these strategies in the exploration of novel organic optoelectronic materials. Finally, the existing problems and development prospect of this area are elaborated.