Benzoin condensation is an important carbon-carbon bond-forming reaction. The benzoin reaction with good yield, high enantioselectivity and broad substrate scope is highly desired in organic synthesis. The intermolecular benzoin condensation catalyzed by bifunctional N-heterocyclic carbenes has been investigated, and the corresponding α-hydroxyketones were obtained with yields up to 76% and enantioselectivities up to 99% ee.