Aqueous film-forming foam (AFFF) used for fuel firefighting contains polyfluoroalkyl substances (PFAS) that have been identified as environmentally persistent and bioaccumulative resulting in phase out of AFFF. Currently, there are no environmentally friendly foams available that can perform at the same level as AFFF. Fuel transport has been recognized as a potential mechanism behind poor fire extinguishment, but the key features are yet unidentified. To fill these knowledge gaps, identifying the properties and features of surfactants used in firefighting foam that will prevent the transport of liquid fuel through the surfactant solution was imperative. To achieve that, this research was performed exclusively on single surfactants that have applications in firefighting foam. Impact of single surfactants on fuel transport was evaluated. Thermodynamics of the interaction between single surfactants and fuel; and kinetics of fuel transport through single surfactant solutions was observed. It was hypothesized that the liquid fuel transport would influence microstructure in the bulk of the surfactant solution. Experiments were conducted for different single surfactant structures. Various methods were applied to identify the microstructure and interfacial properties of surfactants with and without exposure to liquid fuel. The factor affecting microstructure, identified through this study was further used to evaluate the firefighting performance of single surfactants through ignition test. The thermodynamics of the interaction between fuel and single surfactants helped us to understand the fuel transport mechanism and role of micelle on fuel transport. Surfactant and fuel interaction has been studied below, at, and above the critical micelle concentration of surfactants. The effect of surfactant concentration, convection, and surfactant types were observed on the fuel transport. Moreover, an ignition test was conducted to evaluate the firefighting performance of single surfactants for various fuel types. Overall, the findings from this study will help design a new type of superefficient, environmentally acceptable surfactant for firefighting foam application. / Doctor of Philosophy / Aqueous film-forming foam (AFFF) used for fuel firefighting contains fluorinated compounds which are environmentally persistent and bioaccumulative. Therefore, AFFF has been phased out. There are no environmentally friendly foams available as efficient as current AFFF. Researchers have found that fuel transport through surfactant foam solution is the reason for foam collapse and poor fire extinguishment performance. However, the key parameters affecting fuel transport through foam solution have not been identified. Therefore, new formulations have become challenging, and it is important to identify the parameters affecting fuel transport through the firefighting foams. Surfactants are the key components of firefighting foam. The liquid fuel transport affects the microstructure of the surfactants in the bulk solution. Through this research microstructural and interfacial properties of single surfactants have been studied with and without exposure to liquid fuel. The factors affecting microstructure and firefighting performance of surfactants have been identified. Moreover, the interaction between fuel and single surfactants has been evaluated. The effect of surfactant concentration and fuel type on fuel transport has been observed. Moreover, the effect of convection (at the foam-fuel interface) on fuel transport has been observed. Overall, an understanding of factors affecting fuel transport of firefighting foam is achieved through this research, which can guide new types of efficient, environmentally friendly surfactant design.