The preparation of enantiomerically pure compounds (EPC) is a continuous social demand due to the clinical advantages that enantiopure drugs offer over the racemic forms. Here, the bestwell-established synthetic strategies to access to single-enantiomer compounds are briefly described and compared. In particular, the enantioselective catalysis is introduced paying special attention to the organocatalysis, an emerging and fruitful area in the EPCsynthesis.Of particular interest is the use of small organic molecules as catalysts in cascade reactions. Organocascade reactions involve the formation of several chemical bonds andoften generate stereogenic centers with excellent stereoselectivity. Such one-pot reactions avoid time-consuming and costly step-bystepprocesses and are environmentally friendly as they occur in the absence of metals. Additionally, the chemical waste of theorganocatytic cascade reactions is drastically reduced since the intermediates are not isolated and purified.