Solvation in aqueous electrolyte solutions and at interfaces still has many questions remaining despite being prevalent throughout the energy and water remediation industries. The electrical double layer is where many important dynamical processes such as catalysis and electron transfer occur. The goal of this thesis is to study solvation through development of vibrational probes, and the electrical double layer with two-dimensional infrared (2D IR) spectroscopy to experimentally access the details of the structural dynamics of this complex environment. However, there are several experimental challenges to applying 2D IR spectroscopy to this application, such as assuring the surface specificity of the spectrum, optimizing the signal strength while minimizing spectral distortions from dispersion and Fano lineshapes, and selecting electrode materials that are both sufficiently IR compatible and conductive. Here we will discuss various considerations when designing 2D IR experiments of electrode interfaces, utilizing several substrates and experimental configurations and demonstrate a robust method for 2D IR experiments of electrode interfaces under applied potential that combines non-conducting Si ATR wafers with conductive ITO and thin nanostructured films of plasmonically active Au functionalized with thiol monolayers. We show that layered electrodes on thin Si ATR wafers with thiol monolayers are sensitive to applied potential, and that the distortions in the linear and 2D IR spectra are heavily dependent on the morphology of the Au surface. Additionally, interpretation of spectra taken at the interface is a complex question, and we also discuss possible interpretations in this thesis, as well as suggest future studies that could help to elucidate structural and dynamical processes at the electrochemical interface. Overall, the findings in this thesis contribute to the broader field of electrochemistry and spectroscopy, offering new tools and methodologies for probing interfacial phenomena at the molecular level.