To better understand the influence of electrolyte chemistry on the ion-desolvation portion of charge-transfer beyond the commonly applied techniques, we apply free-energy sampling to simulations involving diethyl ether (DEE) and 1,3-dioxoloane/1,2-dimethoxyethane (DOL/DME) electrolytes, which display bulk solvation structures dominated by ion-pairing and solvent coordination, respectively. This analysis was conducted at a pristine electrode with and without applied bias at 298 and 213 K to provide insights into the low-temperature charge-transfer behavior, where it has been proposed that desolvation dominates performance. We find that, to reach the inner Helmholtz layer, ion-paired structures are advantageous and that the Li+ ion must reach a total coordination number of 3, which requires the shedding of 1 species in the DEE electrolyte or 2-3 species in DOL/DME. This work represents an effort to predict the distinct thermodynamic states as well as the most probable kinetic pathways of ion desolvation relevant for the charge transfer at electrochemical interphases.