Enantioselective liquid chromatography remains an important technology in modern drug discovery to support the establishment of activity profiles of chiral drug candidates. Likewise, it is increasingly gaining on importance in the field of food chemistry, environmental analysis of chiral pollutants and various other fields. A great number of chiral stationary phases (CSPs) have been developed which allow separation of virtually any racemate. Detailed understanding of the underlying principles and mechanisms of chiral recognition of these CSPs is often underdeveloped amongst users, but is important in the course of development and optimization of enantiomer separations in LC and SFC. In this tutorial an overview of the state-of-the-art in LC enantiomer separation will be presented with specific focus on mechanistic aspects, such as direct and indirect approaches of enantiomer separation, basic chiral recognition mechanisms of modern chiral stationary phases, thermodynamics, additivity principle of binding increments, site-selective thermodynamics, and extrathermodynamic approaches. Emphasis will be put on the most frequently employed commercial CSPs and mobile phase systems, including reversed-phase, normal-phase, polar organic and supercritical fluid operational modes. This overview will cover CSPs based on (i) chiral polymers (proteins, polysaccharides, and synthetic polymers), (ii) macrocycles (macrocyclic antibiotics, cyclodextrins, cyclofructans, crown ethers), (iii) donor-acceptor (Pirkle) type chiral synthetic selectors, chiral ion exchangers, and chiral ligand exchange selectors. Recent trends as well as aspects and problems arising in practical applications will be discussed in more detail.