The implication of chirality in pharmaceuticals is briefly reviewed, presenting the basic concepts and the chiral recognition phenomenon in biological systems. The importance to recognize enantiomers of chiral pharmaceuticals, both in pharmacology and environmental fields, is emphasized and many examples were selected to demonstrate the significance of chirality in both areas. Methodologies to obtain single enantiomers and to control the enantiomeric fraction associated with enantioseparation of chiral pharmaceuticals are also discussed. Several enantioselective methods using liquid chromatography (LC) with chiral stationary phases (CSPs) in biomedical and environmental fields are presented. The most used CSPs, their advantages and drawbacks, are swiftly revised.