Abstract The regioselectivity of C−H functionalization is commonly achieved by directing groups, electronic factors, or steric hindrance, which facilitate the identification of reaction sites. However, such strategies are less effective for reactants such as simple monofluoroarenes due to their relatively low reactivity and the modest steric demands of the fluorine atom. Herein, we present an undirected gold‐catalyzed para ‐C−H arylation of a wide array of monofluoroarenes using air‐stable aryl silanes and germanes at room temperature. A high para ‐regioselectivity (up to 98 : 2) can be realized by utilizing a dinuclear dppm(AuOTs) 2 (dppm=bis(diphenylphosphino)methane) as the catalyst and hexafluorobenzene as the solvent. This provides a general and practical protocol for the concise construction of structurally diverse para ‐arylated monofluoroarenes through C−H activation manner. It features excellent functional group tolerance and a broad substrate scope (>80 examples). Besides, this strategy is also robust for other simple monosubstituted arenes and heteroarenes. Our mechanistic studies and theoretical calculations suggest that para ‐C−H selectivity arises from highly electrophilic and structurally flexible dinuclear Ar−Au(III)−Au(I) species, coupled with noncovalent interaction induced by hexafluorobenzene.