These studies examine how various latex copolymer compositions, ranging from 100% n-BA to 50%/50% Sty/n-BA, may influence sodium dioctylsulfosuccinate (SDOSS) mobility, diffusion, and orientation near the film-air (F-A) and film-substrate (F-S) interfaces. Polarized attenuated total reflection Fourier transform infrared spectroscopy is utilized to examine the surfactant behavior in Sty/n-BA latexes at the F-A and F-S interfaces. Based on the analysis developed for the purpose of these studies, the highest concentration of SDOSS is detected near the F-A interface far 50%/50% Sty/n-BA compositions. However, when the content of styrene in Sty/n-BA copolymer is diminished, the highest content of SDOSS is detected near the F-S interface. This behavior is particularly evident for 100% poly(n-BA) latexes. When SDOSS molecules are near the F-A and F-S interfaces, the SO3-Na+ hydrophilic ends are preferentially parallel to the surface, whereas hydrophobic tails are perpendicular.