New-generation lithium-ion batteries use ionic liquids (ILs) as electrolyte solutions, greatly enhancing the safety and energy storage capacity of the battery. Fundamental molecular insights are useful for understanding the advantages of high conductivity of IL solvent electrolytes over organic solvent ones. In this work, we computationally studied two organic solvents (DMC and DEC) and four IL solvents ([Cnmim][BF4] and [Cnmim][TFSI] (n = 2, 4)) to examine the physicochemical properties of high concentration electrolytes. As expected, the IL solvent electrolytes exhibit higher density and viscosity, and larger self-diffusion coefficients and conductivity than the organic solvent electrolytes. Further, the microstructures of the lithium salt LiTFSI in various solvent electrolytes were investigated to explore the effect of the organic and IL solvents on the ionic association of the ions Li+ and TFSI-. The structural analysis of LiTFSI revealed that the organic solvents restrict the free motion of the ions, reducing the conductivity of the electrolytes. The [BF4]-type IL electrolytes have higher conductivity than the [TFSI]-type IL electrolytes, especially [C4mim][BF4] with the highest conductivity among the IL-based electrolytes. More importantly, it was proved that the dissolution of LiTFSI in the IL solvents is an anion-driven process.