Surfactants are fundamental in personal care products, offering diverse functionalities such as cleansing, foaming, emulsification, solubilization, conditioning, thickening, and perfume stabilization. Their amphiphilic nature enables them to interact with both hydrophilic and hydrophobic substances, making them indispensable in the formulation of shampoos, body washes, lotions, and cosmetics. This chapter provides a comprehensive overview of surfactant classification—encompassing both natural (biosurfactants) and synthetic types—along with their structural variations based on ionic nature and hydrophobic tail composition. Recent advancements in surfactant science are emphasized, including the development of fluorocarbon and silicone-based surfactants with superior wetting and spreading capabilities. The growing shift toward biodegradable, bio-based, and sulfate-free alternatives is explored in response to increasing environmental and dermatological concerns. Emerging applications, such as nanoemulsions for enhanced delivery, biosurfactants for green formulations, and smart surfactants responsive to stimuli, are also discussed. By addressing both the functional diversity and sustainability challenges of surfactants in personal care, this chapter not only reflects current industry trends but also outlines future directions for innovation in surfactant technology.