In addition to the brilliant chiral phosphorus metal catalysts, chiral phosphine-free metal complexes find increasing application as catalysts for asymmetric hydrogenation. In this account, two types of chiral phosphine-free ligands, N-heterocyclic carbene-based C,N-ligands and diamine-based N,N-ligands, in the homogeneous asymmetric hydrogenation of prochiral ketones, imines and quinolines are reviewed.