A novel rotaxane-type asymmetric catalyst that displays its function through the cooperative effect of the components was designed and synthesized to evaluate its catalytic activity in the O-acylation of meso-1,2-diol. The catalyst efficiently catalyzed the selective monobenzoylation of meso-1,2-hydrobenzoin to afford both 99% yield and 98% ee. The cooperative working of the two components is essential for the excellent reactivity and enantioselectivity.