Understanding and controlling crystal surfaces is a critical problem in contemporary materials science. Organic crystal surfaces present the additional complexity of multiple terminations with different functional groups. These alternate terminations influence the surface chemistry and exert control over many material properties. While established tools for surface characterization exist, few provide the chemical information required to unambiguously identify functional groups. Polarized Raman spectroscopy is a versatile tool that can provide detailed chemical information on molecular materials, and, when used in a microscope configuration, can be used to map substrates on a micron scale. In this work, we demonstrate the use of polarized Raman to study the surface chemistry of aspirin. By analyzing crystals grown under a variety of conditions, we relate the growth solvent to the surface termination and reconcile the conflicting results in the literature on the nature of the <100> surface. Our results are supported by detailed first-principles modeling of the surfaces and their vibrational spectra. This study establishes the potential of polarized Raman microscopy as a tool for organic surface science that, when combined with predictive modeling, provides a powerful means to understand and ultimately control surface chemistry.