Asymmetric ring-opening polymerization of lactides is more concerned due to wide PLA application. In recent years, organometallic catalysts are applied to ring-opening polymerization of lactides and provided for well controlling the microstructure of PLA formed from polymerization. The study of controlling side reactions such as intermolecular and intramolecular transesterification is well established but asymmetric polymerization with highly stereoselectivity is less. The high stereoselective polymer could not be produced by chiral centers or bulky steric hindrance function groups of catalysts during the polymerization process. In this report, we will introduce the related information and the latest research.