Sulfone–ester mixed solvent electrolytes were examined for 5V-class high-voltage rechargeable lithium cells. As the base-electrolyte, sulfolane (SL)–ethyl acetate (EA) (1:1 mixing volume ratio) containing 1M LiBF4 solute was investigated. Electrolyte conductivity, electrochemical stability, Li+ ion solvation behavior and cycleability of lithium electrode were evaluated. 13C NMR measurement results suggest that Li+ ions are solvated with both SL and EA. Charge–discharge cycling efficiency of lithium anode in SL–EA electrolytes was poor, being due to its poor tolerance for reduction. To improve lithium charge–discharge cycling efficiency in SL–EA electrolytes, following three trials were carried out: (i) improvement of the cathodic stability of electrolyte solutions by change in polarization through modification of solvent structure; isopropyl methyl sulfone and methyl isobutyrate were investigated as alternative SL and EA, respectively, (ii) suppression of the reaction between lithium and electrolyte solutions by addition of low reactivity surfactants of cycloalkanes (decalin and adamantane) or triethylene glycol derivatives (triglyme, 1,8-bis(tert-butyldimethylsilyloxy)-3,6-dioxaoctane and triethylene glycol di(methanesulfonate)) into SL–EA electrolytes, and (iii) change in surface film by addition of surface film formation agent of vinylene carbonate (VC) into SL–EA electrolytes. These trials made lithium cycling behavior better. Lithium cycling efficiency tended to increase with a decrease in overpotential. VC addition was most effective for improvement of lithium cycling efficiency among these additives. Stable surface film is formed on lithium anode by adding VC and the resistance between anode/electrolyte interfaces showed a constant value with an increase in cycle number. When the electrolyte solutions without VC, the interfacial resistance increased with an increase in cycle number. VC addition to SL–EA was effective not only for Li/LiCoO2 cell with charge cut-off voltage of 4.5V but also for Li/LiNi0.5Mn1.5O4 cells even with high charge cut-off voltage of 5V in Li/LiNi0.5Mn1.5O4 cells.