My research group is broadly interested in spectroscopically determining how local chemical environments affect single molecule behaviors. We focus on highly heterogeneous systems such as molecular self-assembly and bimetallic catalysis, developing and using new imaging and spectroscopic approaches to probe structure and function on nanometer length scales. This talk will focus on Tip-Enhanced Raman Spectroscopy (TERS), which affords the spatial resolution of traditional Scanning Tunneling Microscopy (STM) while collecting the chemical information provided by Raman spectroscopy. By using a plasmonically-active material for our scanning probe, the Raman signal at the tip-sample junction is incredibly enhanced, allowing for single-molecule probing. This method, further aided by the benefits of ultrahigh vacuum, is uniquely capable of obtaining (1) single molecules chemical identification; (2) the molecular mechanism of chemical bond formation under near-surface conditions using self-assembly concepts; (3)adsorbate-substrate interactions in the ordering of molecular building blocks in supramolecular nanostructures. By investigating substrate structures, superstructures, and the adsorption orientations obtained from vibrational modes, we extract novel surface-chemistry information at an unprecedented spatial (<1nm) and energy (<10 wavenumber) resolution. We are able to interrogate the impact of changes in the chemical environment on the properties of supramolecular nanostructures, and thereby lay the foundation for controlling their size, shape and composition.