Rhodium-catalysed cross-dehydrogenative coupling (CDC) has received considerable attention in recent years. This modern technology has been considered as an attractive synthetic tool for selective C−C bond formation due to (1)...

The advancement of CH/CH cross‐dehydrogenative coupling (CDC) reactions for the construction of C(sp 2 )C(sp 2 ) bond with representative examples from mainly 2016 to May 2021 is overviewed. Palladium‐catalyzed CDC reaction has been considered as a modern and attractive synthetic tool due to (i) limited amount of undesired and toxic by‐products; (ii) more straightforward synthetic approach from simple materials, resulting in a better step‐ and atom economy. Diversified applications across pharmaceutical and material areas have been successfully realized. In addition to the ordinary CDC reaction, the most recent accomplishments of asymmetric CDC process are also included.