Whereas recent synthetic studies concerning Rh-catalyzed olefin hydrogenation based on BINOL-derived monodentate phosphites have resulted in an efficient and economically attractive preparative method, very little is known concerning the source of the unexpectedly high levels of enantioselectivity (ee often 90-99%). The present mechanistic study, which includes the NMR characterization of the precatalysts, kinetic measurements with focus on nonlinear effects, and DFT calculations, constitutes a first step in understanding this hydrogenation system. The two most important features which have emerged from these efforts are the following: (1) two monodentate P-ligands are attached to rhodium, and (2) the lock-and-key mechanism holds, in which the thermodynamics of Rh/olefin complexation with formation of the major and minor diastereomeric intermediates dictates the stereochemical outcome. The major diastereomer leads to the favored enantionneric product, which is opposite to the state of affairs in classical Rh-catalyzed olefin hydrogenation based on chiral chelating diphosphines (anti lock-and-key mechanism as proposed by Halpern).