Herein, we present the Pd(II)-catalyzed atroposelective C-H acyloxylation strategy for the assembly of biaryl aldehyde atropoisomers using readily available amino acids as the catalytic auxiliary and chiral pool. This strategy exhibits a broad substrate scope with a good yield (≤90%) and excellent enantioselectivity (≤99%), furnishing functionalized aldehydes through direct asymmetric C-H oxidation. The application utility of this method was demonstrated by the concise synthesis of a kind of atropoisomeric amino-phenol organocatalyst, which enables good enantiocontrol in catalyzing asymmetric addition of diethylzinc to aldehydes.