An efficient enantioselective acylative desymmetrization of cyclic meso-1,3-diols was developed by using a chiral DMAP derivative 1ehaving a 1,1'-binaphthyl unit. The reactions required only 0.5 mol % of the catalyst and showed good to excellent enantioselectivity. With this transformation, 5a, a key building block for the synthesis of natural products, was easily obtained in almost enantiomerically pure form after a single recrystallization. Control experiments revealed that tert-alcohol units on the catalyst were responsible for both the catalytic activity and enantioselectivity.An efficient enantioselective acylative desymmetrization of cyclic meso-1,3-diols was developed by using a chiral DMAP derivative 1ehaving a 1,1'-binaphthyl unit. The reactions required only 0.5 mol % of the catalyst and showed good to excellent enantioselectivity. Control experiments revealed that tert-alcohol units on the catalyst were responsible for both the catalytic activity and enantioselectivity.