A new strategy for the sequential C–H oxidation/asymmetric phosphonylation of primary alcohols has been developed. It involves a combination of Cu(I)/TEMPO/NMI (N-methylimidazole) oxidation, under an air atmosphere, with chiral Al (salalen)-catalyzed enantioselective addition. Various primary alcohols, including benzylic alcohols, allylic alcohols, propargylic alcohols, alkyl alcohols, and other alcohols containing oxygen-, sulfur-, and nitrogen-heterocycles were smoothly converted into chiral α-hydroxy phosphonates with good yields and high enantioselectivities. Inhibitor of CD45 and a plant growth regulator can be easily synthesized by this new method. A new strategy for the sequential C–H oxidation/asymmetric phosphonylation of primary alcohols has been developed. Various alcohols were smoothly converted into chiral α-hydroxy phosphonates with good yields and high enantioselectivities. Display omitted .