Polarized attenuated total reflection Fourier transform infrared (ATR FT–IR) spectroscopy was used to identify the mobility and surfactant exudation of sodium dioctyl sulfocuccinate (SDOSS) surfactant molecules to the film–air (F–A) and film–substrate (F–S) interfaces in styrene/n-butyl acrylate (Sty/n-BA) latex films. It was found that, depending upon the latex particle composition, the surfactant molecules could be driven to the F–A or F–S interfaces. The primary factors that governed the direction of exudation were the compatibility of the latex components, interfacial film-substrate surface tension, and the chemical composition of the latex particles. Concentration, as well as orientation, of the hydrophilic SONa+ surfactant ends changed as a function of depth and the latex particle composition. © 1993 John Wiley & Sons, Inc.