The enantioselective silylation of racemic alcohols, where one enantiomer reacts faster than the other, is an alternative approach to established enzymatic and non-enzymatic acylation techniques. The existing art is either limited to structurally biased alcohols or requires elaborate catalysts. Simple substrates, such as benzylic and allylic alcohols, with no coordinating functionality in the proximity of the hydroxy group have been challenging in these kinetic resolutions. We report here the identification of a broadly applicable chiral catalyst for the enantioselective dehydrogenative coupling of alcohols and hydrosilanes with both the chiral ligand and the hydrosilane being commercially available. The efficiency of kinetic resolutions is characterized by the selectivity factor, that is, the ratio of the reaction rates of the fast-reacting over the slow-reacting enantiomer. The selectivity factors achieved with the new method are good for acyclic benzylic alcohols (≤170) and high for synthetically usefully cyclic benzylic (≤40.1) and allylic alcohols (≤159).