The influence of copolymer structure on the magnitude of surfactant enrichment to the film—air and film—substrate interfaces of latex films prepared on a polytetrafluoroethylene (PTFE) substrate is investigated. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR FTIR) is used to elucidate the surfactant enrichment by the comparison of butyl acrylate/methyl methacrylate/methacrylic acid (BA/MMA/MAA) and ethyl acrylate/methacrylic acid (EA/MAA) latex systems prepared with various anionic surfactants. It is found that, in all cases, the magnitude of exudation of the sulfonate-containing surfactants manifested by the presence of S—O bending and scissors modes is reduced in the case of the BA/MMA/MAA latex. Similar behavior is observed when the spectra of films prepared on a liquid mercury substrate are compared. It is believed that this behavior results from the longer aliphatic n-butyl groups present in this copolymer that enhances compatibility by providing a greater opportunity for hydrophobic surfactant—copolymer interactions. The butyl groups may also reduce excess interfacial free energy by orienting themselves toward the film interfaces, which, in turn, will reduce the surface tension-induced driving force for surfactant exudation. © 1993 John Wiley & Sons, Inc.