This study focuses on the behavior of sodium dioctylsulfosuccinate (SDOSS) in 50/50 w/w % polystyrene/poly(butyl acrylate) (p-Sty/p-BA) latex films. Specifically, mobdity and orientation are examined in the context of the film formation by the use of dynamic mechanical thermal analysis and attenuated total reflectance (ATR) Fourier transform infrared (FT-IR) spectroscopy. While for the homopolymer blends of p-Sty and p-BA, two T8 values resulting from a phase separation of p-Sty and p-BA phases are observed, only a single Tg is detected for a copolymer of the same mixture, indicating a single phase within the film. ATR FTIR spectroscopic data indicate that the phase separation of p-Sty and p-BA blends does not occur uniformly across the film. After coalescence, p-Sty particles produce a significant degree of stratification at approximately 1.6 pm from the film surface. At this depth, the polystyrene rings assume preferentially parallel orientation to the film surface. At the same time, the hydrophilic groups of SDOSS surfactant(SO;Na+) are orientedpreferentiallyparallelto the surface.Under high relative humidity conditions, water is able to diffise into the film and swells the surface layers, thus causing them to expand. As a result, the top, predominately poly-n-BA surface becomes "thicker," and p-Sty phase appears to be near 2.3 pm from the surface. The polystyrene rings maintain their preferential parallel orientation to the surface, but the hydrophilic groups of SDOSS are able to diffise into the film with the water uptake and are thus not present at the film-air interface.