An effective synthesis of chiral atropoisomeric biaryl phosphine–olefin compounds via palladium-catalyzed enantioselective C–H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R₂ not only acts as the directing group to direct C–H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.