Amphiphiles form a large group of supramolecular structures can aggregate and be adsorbed spontaneously at the interface. Amphiphilicity is a feature of polar contrast between the groups that make up a molecule and their spatial separation. The most important classes of amphiphiles are surfactants, lipoproteins, and polymers that have hydrophilic and hydrophobic chemical moieties covalently bonded and spatially separated. Since surfactants are widely used in various industrial fields, we decide to focus on surfactants in addition to a brief review of the other amphiphiles. Surfactants are used in industrial applications and consumer products, from medical to cosmetics and food industry. Various industries require new surfactants from sustainable and renewable raw materials with improved performance, biocompatibility and minimal environmental impact. For example, liquid phase exfoliation and dispersion methods using surfactants in the solvent media have recently gained lots of attention because of their great potential for large-scale production. Notably, an ideal exfoliation for reaching desired graphene and CNTs may be achievable by molecular engineering of surfactants to improve the quality of molecular interactions. This chapter experimentally and theoretically highlighted physico-chemical characteristic parameters, and interactions of the components, which are essential to design and discover efficient exfoliation and dispersion systems.