This article describes the procedure for gold‐catalyzed oxidative coupling of arenes and arylsilanes. It presents some of the important points to be considered, the conditions that need to be maintained, characterization data, and the reagents required, as well as the techniques used and the equipment setup that are vital to carrying out the process. The chapter provides an overview, the scope and limitations of intermolecular and intramolecular coupling of arenes and aryl silanes and intermolecular coupling of heteroarenes and aryl silanes. It also presents a detailed procedure for the preparation and cyclization of 1‐trimethylsilyl‐2‐(phenoxymethyl)benzene as a general example for the arylation of aryl silanes. The article also describes the hazards associated with working with chemicals and the ways to deal with these hazards.