Enantioselective hydrogenation by heterogeneous catalysts has gained great importance in organic synthesis, chemical engineering and pharmaceutical industry. However, the mechanism of enantioselectivity is not well understood due to the absence of evidence at the molecular level. Recently, the great advance on this topic has been made by applying scanning tunneling microscopy (STM) and other surface characterization techniques to get direct evidence about the enantioselective mechanism of catalysts. Here, the progress on the adsorption mode of chiral modifiers such as cinchona and tartaric acid and the related enantioselective mechanism is reviewed from the viewpoint of surface science. Particularly, some STM works on this topic are summarized. Finally, several key issues for further investigation are outlined.