Since the introduction of Lithium-ion batteries (LIBs) into commercial use, great improvements have been achieved in their performance such as energy density, durability, and safety. However, there still remain many technical issues to meet the increasing demands for a longer driving range of electric vehicles, a larger storage for renewable energy. Research and development of electrode active materials are extensively progressing to respond those market needs, and R&D for electrolyte solutions are also active in order to utilize the fullest extent of the newly developed electrode materials.Various kinds of characteristics are required for electrolyte solutions in LIBs. Ideally, the electrochemical stability in a wide potential range is needed, but almost all the electrolyte solutions reductively decompose on negative electrodes, and the decomposition products precipitate on the electrode to form a protective surface film, which is referred to as SEI (solid electrolyte interphase). Because the nature of SEI is influenced by chemical structures of electrolyte solutions, the solvents and lithium salts need to be combined properly to realize LIBs with better performance. Although the conventional electrolyte solutions show satisfactory performance to some extent, there still remain some disadvantages; instability against moisture and temperature, and volatility and flammability of carbonate ester solvents. Great efforts have been made to overcome those disadvantages in the conventional electrolyte solutions, for example, utilization of ionic liquid, polymer electrolytes and inorganic solid state electrolytes, and recently, highly concentrated electrolyte solution gathers a lot of attention.Based on these background, solid electrolyte interphase (SEI) formed on graphite in conventional and highly concentrated electrolyte solutions was thoroughly characterized by a combined experimental and computational study. The comprehensive understanding revealed that a chemical composition of SEI, as well as the solvation structures unstable to reductive potential, can be predicted by a profound understanding of density functional theory (DFT) calculation results of the solvates containing a counter anion. The solvation structures were determined by Raman spectroscopy to evaluate electron affinity (EA) and LUMO of the solvates containing an anion by DFT calculation. The chemical composition of SEI was quantitatively analyzed by X-ray photoelectron spectroscopy (XPS), and the results were compared with a prediction based on the calculation. The formation mechanism of SEI during charge and discharge process can be partly estimated by the combination of experiment and theoretical calculation. These results indicate that electrolyte solutions can be efficiently designed by predicting the physicochemical properties of SEI through the more effective utilization of DFT calculation. Thus, a combination of DFT prediction and experimental analysis is proved to be an effective approach to reveal SEI formation mechanisms, and can be utilized as a versatile approach to develop new solvents, electrolyte salts, and additives, and to design electrolyte solutions with appropriate concentration.It is expected that the oxidative stability and reaction mechanism of electrolyte solutions at the positive electrode can be estimated using similar approaches. Here, it is necessary to predict oxidative stability using ionization potentials (IP), rather than EA. In the same way, other solvents than carbonate, such as ethers and sulfones, which have been difficult to put into practical use in conventional electrolytes, can also be the target to be studied. By analyzing the solvation structure and estimating its chemical stability, we believe it will be possible to get many insights on the reactions that proceed at the interface between the electrode and the electrolyte. Figure 1