The site-selective acylations of β-hydroxyamides in the presence of other hydroxyl groups are described. Central to the success of this modification is the metal-template-driven acylation using pyridine ketoxime esters as acylating reagents in combination with CuOTf. This strategy enables β-hydroxyl groups to be site-selectively acylated in various derivatives, including sterically hindered secondary β-alcohol. The utility of this methodology is showcased by the serine-selective modification of a glycopeptide with unprotected sugar.