Organocatalytic enantioselective hydrophosphonylation of ketimines using cinchona alkaloids and Na2CO3 afforded products with high enantioselectivity. Both enantiomers of alpha-amino phosphonates can be prepared by using pseudoenantiomeric cinchona alkaloids. The catalyst loading of cinchona alkaloids can be reduced to 0.5 mol % without a significant loss of enantioselectivity.