Small molecules and polymers with conjugated structures can be used as organic optoelectronic materials. These molecules have conventionally been synthesized by cross-coupling reactions; however, in recent years, direct functionalization of C-H bonds has been used to synthesize organic optoelectronic materials. Representative reactions include direct arylation reactions (C-H/C-X couplings, with X being halogen or pseudo-halogen) and cross-dehydrogenative coupling (C-H/C-H cross-coupling) reactions. Although these reactions are convenient for short-step synthesis, they require regioselectivity in the C-H bonds and suppression of undesired homo-coupling side reactions. This review introduces examples of the synthesis of organic optoelectronic materials using two types of direct C-H functionalization reactions. In addition, we summarize our recent activities in the development of direct C-H functionalization reactions using fluorobenzenes as substrates. This review covers the reaction mechanism and material properties of the resulting products.