A multiscale stability study of foams stabilized by sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS), and sodium polyoxyethylene alkylether sulfate (AES) was conducted, to investigate the relationship of surfactant molecular behavior and interfacial monolayer configuration of foam film to the foam film properties. Molecular dynamic (MD) simulations using a full-atom model was utilized to explore the microscopic features of the air/liquid interface layer. Several parameters such as the distribution of surfactant head groups and the order degree of surfactant hydrophobic tails were used to describe the molecular adsorption behavior. The effect of molecular structure on the nature of the foam film and the impact on the dynamic stability of wet foam is discussed. In the experimental evaluation, the SDBS foam films manifest strong stiffness and low viscoelasticity as shown by the interfacial shear rheology determination as well as texture analyzer (TA) measurement results, which agree very well with the array behavior of SDBS molecules at the air/water interface as described by the simulation results and is identified to be the reason for the poor dynamic stability. Comparing the molecular structure of SDS, SDBS, and AES, the special contributions of the linking groups such as the 0 atom, the phenyl group, and the EO (oxyethyl) chain to the interfacial array behavior of surfactants were characterized. It is concluded that microhardness of the foam film enhanced by rigid linking groups favors static foam stability but decreases the dynamic foam stability, while viscoelasticity of the foam film enhanced by soft linking groups increases the dynamic foam stability.