This chapter is intended to provide a comprehensive overview of the chemistry and molecular structures of cholesterol-based low molecular mass organogelators and to describe the underlying principles that are responsible for self-assembly and, in turn, organogel formation within this important class of systems. In particular, the properties of the resulting organogels are discussed in terms of the relationship between the designed structure of the gelator, the nature of the gelled organic fluid component, the influence of molecular interactions (π-π stacking, Van der Waals, hydrogen bonding, …), and chirality. Emphasis is given to the remarkably high synthetic tunability of the cholesterol-based organogelators, which enable access to a range of functional gels. The prospects for future applications of cholesteryl molecular gels will be illustrated and discussed at the end of the chapter.