Corrosion remains a pervasive issue across various industries, resulting in significant economic and structural challenges. This chapter provides a comprehensive examination of surfactant-based corrosion inhibitors, emphasizing their amphiphilic nature that facilitates adsorption onto metal surfaces, forming protective barriers against corrosive agents. The discussion encompasses the classification of surfactants including anionic, cationic, nonionic, zwitterionic, gemini types, etc. and explores their structure–property relationships pertinent to corrosion inhibition. A comparative analysis between single-component and mixed surfactant systems is presented, highlighting the enhanced efficacy of mixed systems due to synergistic interactions that improve surface coverage and stability. Mechanistic insights into adsorption processes such as physisorption, chemisorption, electrostatic interactions, hydrophobic interactions, and coordinate bonding are provided, considering variables like surfactant charge and type, metal type, pH, temperature, and electrolyte composition. This chapter underscores the industrial relevance of these inhibitors through applications in sectors like oil and gas, marine, aerospace, automotive, and chemical processing. Future perspectives are discussed, focusing on the development of eco-friendly bio-surfactants, nanostructured inhibitors, smart self-healing coatings, and the integration of artificial intelligence for predictive modeling. By bridging theoretical insights with practical applications, this work serves as a valuable resource for researchers and professionals dedicated to advancing sustainable and high-performance anticorrosive technologies.