The morphologies of phase-separated monolayer films prepared from two different binary mixtures of perfluorocarbons and hydrocarbons have been examined and compared, for the,first time, at the solid-air and liquid-air interfaces. Films were comprised of binary mixtures of arachidic acid (C19H39COOH) with perfluorotetradecanoic acid (C13F27COOH) and of palmitic acid (C15H31COOH) with perfluorooctadecanoic acid (C17F35COOH). For both mixed systems, Langmuir Blodgett films on mica substrates consisted of polygonal domains of one surfactant dispersed in a continuous matrix of the other (arachidic acid in perfluorotetradecanoic acid or perfluorooctadecanoic acid in palmitic acid, respectively), consistent with previous reports. Real-time imaging of the air-water interface via Brewster angle microscopy revealed that comparable film morphology was present at the air-water interface and the solid-air interface over a wide range of surface pressures, and that for the arachidic acid-based mixture, domain growth dynamics at the air-water interface is consistent with that inferred from sequential "static" atomic force microscope images collected at the solid-air interface. (C) 2012 Elsevier Inc. All rights reserved.