Fluorescence near-field scanning optical microscopy (FL-NSOM) is used to probe the nanoscale structure in stained phospholipid monolayers deposited on glass substrates at moderate surface pressures. The FL-NSOM images reveal new liquid-expanded (LE) and liquid-condensed (LC) domains, including one-to-one correlation between fluorescence contrast and film topography. In particular, films of the phospholipid DPPC stained with DiIC(12) exhibit multilayer structures that are observed within the solid phase domains and have LE-like fluorescence signals. These features are attributed to clusters of dye molecules resulting from the localized collapse of the film upon compression. Such collapsed features are also observed in supported films of 100% DiIC(12) deposited at high surface pressure. In these films, spatially-resolved spectroscopy shows that the collapsed structures are amorphous based on the fluorescence spectrum while the molecules within the solid phase of the film have a fluorescence spectrum indicative of molecular aggregates.