Surfactants are compounds that have both hydrophilic and hydrophobic properties due to their structures and are widely used in many industrial products, daily life, and many electrochemical studies. The hydrophobic parts usually consist of long hydrocarbon chains, while the hydrophilic parts can contain many different functional groups. These substances, also called surface active agents, reduce the surface tension in their aqueous solutions. For this reason, in addition to their use as emulsifiers, they also have antibacterial properties, are solubilizers, and are used as detergents. Although the use of synthetic surfactants is common in general, biosurfactants, which are called green surfactants, are also being studied intensively. In this chapter, the role of surfactants in electrochemistry is discussed, and their structural properties are also noted. Moreover, different usage areas in electrochemistry and types of surfactants and their properties are given.