The kinetic and morphological properties of the surface layers formed on lithium electrode in different sulfolane‐based electrolytes have been investigated. Application of the impedance theory of the dilute binary electrolyte has allowed a determination of characteristic parameters of the surface layers, such as their cationic transference numbers, salt diffusion coefficients, and ionic concentrations. The values obtained for these parameters have demonstrated that the surface layers behave similarly to their parent liquid electrolytes but with much lower ionic concentrations. In addition, this study has shown that satisfactory cycling performances can be obtained when the values of the characteristic parameters of the layers are close to those of the parent electrolytes. Supplementary tests based on the evaluation of the layer conductivity, the Warburg constant, and the limiting current density, have been proposed for the selection of appropriate organic electrolytes and cycling procedures to be used in secondary lithium batteries.