The first example for asymmetric reaction of diazomethylphosphonates with α-ketoesters was realized in the catalysis of hydroquinidine-derived bifunctional thiourea. A methodology was established to access a series of chiral α-diazo-β-hydroxyphosphonate derivatives containing various functional groups with high enantioselectivities and yields. The resulting products could be further transformed into chiral tertiary β-hydroxyphosphonate and α-halogenated fosfomycin derivatives, especially α-fluoride analogues.