Poly(ε-caprolactone)/polystyrene (PCL/PS) blends, where nonamphiphilic PS is glassy in the bulk state at the experimental temperature of 22.5°C, are immiscible as Langmuir films at the air/water (A/W) interface. Surface pressure-area per monomer isotherm analyses indicate that the surface concentration of amphiphilic PCL is the only factor influencing the surface pressure below the collapse transition. For PS-rich blends, Brewster angle microscopy (BAM) studies at the A/W interface and atomic force microscopy studies on Langmuir-Schaefer films reveal that PS nanoparticle aggregates formed at very low surface pressures can form networks upon further compression. The morphologies seen in PS-rich blends (networklike rings) are consistent with a recent study of a nonamphiphilic polyhedral oligomeric silsesquioxane (POSS), octaisobutyl-POSS, blended with amphiphilic poly(dimethylsiloxane), suggesting that the nonamphiphilic PS aggregates at the A/W interface produce domains with dipole densities that differ from that of pure PCL. In all composition regimes, the amphiphilic PCL phase tends to spread and form a continuous surface layer at the A/W interface, while simultaneously improving the dispersion of nonamphiphilic PS domains. During film expansion, BAM images show a gradual change in the surface morphology from highly continuous networklike structures (PS-rich blends) to broken ringlike structures (intermediate composition) to small discontinuous aggregates (PCL-rich blends). This study provides valuable information on the morphological evolution of semicrystalline PCL-based polymer blends confined in a "two-dimensional" geometry at the A/W interface and fundamental insight into the influence of microstructure (domain size, phase-separated structures, crystalline morphology, etc.) on the interfacial properties of blends as Langmuir films.