This study addresses the effect of particle structure and composition on the mobility and orientation of sodium dioctyl sulfosuccinate (SDOSS) surfactant molecules in polybutyl acrylate/polystyrene core/shell-type latex films near the film-air (F-A) and film-substrate (F-S) interfaces. In an effort to determine how the surface tension of the substrate influences the migration and orientation of the SDOSS surfactant molecules, polytetrafluoroethylene (PTFE) and liquid Hg substrates were used. It appears that, as the concentration of styrene monomer in the latex increases, SDOSS migrates toward the F-A and F-S interfaces. As the surface tension of the substrate changes from 18 mN/m in PTFE to 400 mN/m for liquid Hg, the surfactant also migrates toward the two interfaces. For the latex particles composed of 50%/50% styrene/n-butyl acrylate (Sty/n-BA) latex copolymer, the hydrophilic SO3-Na+ groups of SDOSS surfactant are present primarily near the F-A interface, and they appear to be mostly parallel to the surface for the films cast on the PTFE surface. For the latex films cast on the liquid Hg surface, the SDOSS hydrophilic surfactant groups are found to be preferentially parallel near the F-A interface and perpendicular near the F-S interface. These studies indicate that the surfactant concentration and its orientation throughout the latex film change as a function of the initial monomer composition and the surface tension of the substrate. Furthermore, the SDOSS concentration appears to vary with depth into the latex interfaces.