Ionic liquids exhibit heterogeneous structures in both the normal and parallel planes with respect to an interface. The formation of these structures can be almost instantaneous or require hours to develop. The impact of these structures on molecular diffusion and local chemical environment can be significant, impacting tribology, solvation, and catalysis. Our work uses DC and AC electrochemistry, linear and non-linear spectroscopies, probe and optical microscopies, and thermochemistry to examine the IL structures that form near surfaces and within the electrochemical double layer. We probe the dynamics of the order/disorder transitions and attempt to reconcile experimental deviations from predicted, theoretical behaviors (i.e. capacitance or redox). In this talk, we will present series of DC and AC electrochemical data paired with spectroscopic analysis of ionic-liquid interfaces with electrodes to describe the interfacial, or sometimes micron scale ordered structures we observe in IL solvents. We incorporate redox probe molecules to observe the effects of IL ordering on electron transfer. We also probe how the electrochemical system changes in response to diluting the IL with molecular liquid cosolvents (water or acetonitrile). Finally we extend our studies to the electroreduction of carbon dioxide in IL systems, and present preliminary data on the optimization of a mixed IL+cosolvent system on Ag electrodes.