A new family of neutral, solvatochromic surfactants has been used to probe solvent polarity across strongly associating solid/liquid interfaces. The surfactants consist of p-nitroanisole-based chromophores and polar -OH groups separated by alkyl chains of different lengths. The solid substrate is silanol-terminated, hydrophilic silica, and the strongly associating solvents are 1-butanol and 1-octanol. To understand how the chromophore itself interacts with the hydrophilic substrate, we acquire resonance enhanced second harmonic (SH) spectra of the bare chromophore adsorbed to the silica/cyclohexane, solid/liquid interface. Spectra show two features despite the chromophore having only a single electronic resonance in the wavelength region (similar to300 nm) examined. These features are assigned to the chromophore adsorbed to the surface in two different orientations. Second harmonic spectra of the bare chromophore adsorbed to the hydrophilic/butanol and hydrophilic/octanol interfaces again show two features with the less polar, shorter wavelength feature being more pronounced in the octanol spectrum. Despite exhibiting pNAs-like behavior in bulk solution, molecular rulers present a very different picture of interfacial polarity. SH spectra from the hydrophilic/butanol interface indicate that interfacial polarity is enhanced over bulk solution limits. Furthermore, spectra lose their bimodal appearance, indicating that local polarity is rather uniform across the interfacial region. In contrast, the hydrophilic/octanol interface continues to show bimodal behavior for all of the molecular rulers studied, suggesting that surface-induced changes in solvent structure partitions solvent polarity into regions that are more polar and less polar than bulk solution. Data from the hydrophilic/octanol system suggest that variations in solvent polarity extend no more than similar to1.2 nm into solution or approximately the length of a fully extended, 1-octanol molecule.