Exudation of sodium dioctylsulfosuccinate (SDOSS) surfactant molecules to the film-substrate (F-S) and film-air (F-A) interfaces in styrene/n-butyl acrylate (Sty/n-BA) latex films in the presence of trimethoxysilyl propylmethacrylate (MSMA) molecules was examined by polarized attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy. It appears that SDOSS molecules are present at the F-A interface but are not detected at the F-S interface due to their displacement by MSMA. When the second layer of latex is deposited on the previously coalesced latex film with the same composition, SDOSS molecules are detected at the F-A of the top overlayer and the interfacial regions between both films. While the top film contains SDOSS surfactant molecules in their free or COOH hydrogen-bonded forms, the interfacial regions between the films exhibit arrays of SDOSS molecules preferentially parallel to the film surface.