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Adaptive biasing force molecular dynamics simulations and density functional theory calculations were performed to understand the interaction of Li⁺ with pure carbonates and ethylene carbonate (EC)‐based binary mixtures. The most favorable Li carbonate cluster configurations obtained from molecular dynamics simulations were subjected to detailed structural and thermochemistry calculations on the basis of the M06‐2X/6‐311++G(d,p) level of theory. We report the ranking of these electrolytes on the basis of the free energies of Li‐ion solvation in carbonates and EC‐based mixtures. A strong local tetrahedral order involving four carbonates around the Li⁺ was seen in the first solvation shell. Thermochemistry calculations revealed that the enthalpy of solvation and the Gibbs free energy of solvation of the Li⁺ ion with carbonates are negative and suggested the ion–carbonate complexation process to be …