Owing to their versatile (opto)electronic properties, conjugated polymers have found application in several organic electronic devices. Cross‐coupling reactions such as Stille, Suzuki, Kumada couplings, and direct arylation reactions have proved to be effective for their synthesis. More atom‐efficient oxidative direct arylation polymerization has also been reported for making homopolymers. However, growing interest toward donor‐acceptor polymers has led to the recent emergence of cross‐dehydrogenative coupling (CDC) polymerization to synthesize alternating copolymers without any prefunctionalization of monomers. Metal‐catalyzed cross‐coupling of two simple arenes via double C−H activation, or of an arene with an alkene via oxidative Heck‐type reaction have been used so far for CDC polymerization. In this article, we discuss the development of CDC polymerization protocols along with the relevant small molecule CDC reactions for an improved understanding of these reactions. Cross‐dehydrogenative coupling (CDC) via C−H activation is the latest addition in the repertoire of synthetic strategies towards conjugated polymers. This article captures the development of this polymerization strategy in the light of background small molecule reactions and highlights how its approach is greener than the previous methods. Arene–arene and arene–alkene couplings via transition metal catalysts have been explored for CDC polymerization.