Abstract Atropisomeric biaryls are one of the important motifs which are highly essential in ligands, biologically active molecules, and natural products. For the synthesis of atropisomeric biaryl and vinylarene derivatives, the transition metal‐catalyzed CH functionalization has been documented as a promising strategy. This article is planned to summarize the research in the field of biaryl atropisomer synthesis within the scope of transition‐metal catalyzed CH bond functionalization. Research regarding atroposelectivity in CH activation procedures and the applications of these novel ideas for the improvement of new‐fashioned carbon–carbon and carbon–heteroatom bond‐featuring reactions are described. Throughout this article, a particular emphasis is placed on the development of CH functionalization strategies that are relevant in the reign of atroposelective synthesis of chiral biaryl and vinylarene analogs.