A Pd-catalyzed, asymmetric oxidative cross coupling reaction between ferrocenes and heteroarenes is described. The process, which takes place via a twofold C-H bond activation pathway, proceeds with modest to high efficiencies (36-86%) and high levels of regio- and enantioselectivity (95-99% ee). In the reaction, air oxygen serves as a green oxidant and excess amounts of the coupling partners are not required. The process is the first example of a catalytic asymmetric biaryl coupling reaction that occurs via double C-H bond activation. Finally, the generated coupling products can be readily transformed into chiral ligands and catalysts.