Surfactant-latex molecular level interactions as well as transient effects during latex film formation play an important role in latex technology. This review article focuses on the siloxane effects on anionic sodium dioctylsulfosuccinate (SDOSS) surfactant exudation during latex coalescence and quantitative analysis of SDOSS distribution at the both film-air (F-A) and film-substrate (F-S) interfaces. Attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy was utilized for characterization of the interactions between SDOSS and styrene-butyl acrylate latex copolymers. In addition, studies of SDOSS stratification along with depth-profiling analysis during latex film formation utilizing step-scan photoacoustic (S-2-PAS) FTIR spectroscopy illustrate that SDOSS content is enriched at the F-A interface and decreases as the penetration depth increases across the latex film thickness.