Single molecule spectroscopic methods are used to obtain detailed information on the polarity and rigidity of molecular-scale environments found in thin poly(vinyl alcohol) (PVA) and poly(methyl methacrylate) (PMMA) films. Nile Red is employed as a highly sensitive spectroscopic probe of environmental properties in these experiments. Fluorescence spectra are recorded fur numerous single molecules and their peak positions and widths determined by fitting the spectra to Gaussian functions. The spectral data are analyzed using a new model for the dependence of the Nile Red charge-transfer transition on the properties of the surrounding medium. This model is based on previous work by Marcus (Marcus, R. A, J. Phys. Chem. 1990, 94, 4963). Additional information required for the analysis is obtained fi om extensive bulk solution-phase absorption and fluorescence studies. A broad inhomogeneous distribution of environments is found fur PVA. The results are shown to depend significantly on PVA film water content, with the results for hydrated films indicating the presence of less rigid environments. In contrast to the PVA results, two distinct classes of environments are found in the PMMA films. On the basis of an analysis of the data using the aforementioned model, it is concluded that the two environments differ in rigidity but have nearly identical polarity.