The use of C1 molecules as feedstocks for producing high-value chemicals is an attractive yet technically inefficient process. Optically pure α-arylglycines are valuable pharmaceutical intermediates, but their efficient asymmetric biosynthesis from C1 molecules has not been reported. Herein, a multienzyme biosynthetic pathway was successfully designed and implemented for the asymmetric synthesis of α-arylglycines from the C1 molecule formaldehyde (HCHO) and aromatic aldehydes, which involved thi