Abstract A concise synthesis of axially chiral biaryl aldehydes through Pd/amino acid‐catalyzed atroposelective interannular C−H arylation of biaryl aldehydes with aryl iodides is developed. This reaction proceeds smoothly involving excellent enantiocontrol and accomplishes with good tolerance of functional groups. Moreover, the readily accessible scale‐up synthesis and further transformation of products has highlighted the potential utility of this asymmetric catalytic protocol. magnified image