Fatty acid microspheres have been used for taste masking purposes whereby the drug is preferentially released in the lower gastrointestinal tract, although the mechanisms involved are poorly understood. In this study, we use a combination of surface pressure measurements, Brewster angle microscopy (BAM) and neutron reflectivity measurements to study the phase miscibility and escaping tendency from mixed stearic and palmitic acid films with a view to relating this to drug dissolution behaviour. It was noted that mixed systems showed considerably greater film interaction and instability than those composed of the pure lipid, especially in alkaline media. BAM studies were able to identify a range of phase separated structures for both the pure and mixed systems. Neutron reflectivity studies indicated a marked selective dissolution of palmitic acid into the subphase as a function of time and allowed quantification of the rate of dissolution of this species. It is concluded that the fatty acids are interacting within the monolayer and in addition the palmitic acid is escaping the mixed monolayers and dissolving into the alkali subphase. These findings have strong relevance for understanding the mechanism of drug release from the associated microspheres.