The electrolytes diluted with fluorinated solvents show promising properties toward better battery technology than existing ones. The transport of Li ions in these fluorinated electrolytes is essential to access the performance of a battery. It is believed that the transport of the Li ion in these electrolytes occurs through polar solvents in the matrix of nonpolar solvent molecules. The atomistic details of this mechanism are yet to be proved using the dynamics of these mixtures. In this study, we performed classical molecular dynamics simulations at various temperatures to probe this mechanism through the structure and dynamics of electrolytes at the atomic level. Here, we have shown that the polar fluorinated solvents assist the Li-ion transport in a region of nonpolar solvent. Highly polar molecules also solvate the Li ion at a lower temperature. The nonpolar solvent solvates the Li ion weakly as compared to others. The calculated values of the ionic conductivity from the Green-Kubo relation provide a better match than that from an experimental conductivity meter. Furthermore, we probed the heterogeneity in the dynamics of the electrolytes by calculating the non-Gaussian parameter. We also show that the transport mechanism of the Li ion in diluted concentrated electrolytes is different than a few of the other reported electrolytes. We have also calculated the ion-pair and ion-cage lifetimes to see the most and least lived ion/ion-solvent pairs. The mechanism given from the present study may help to design the fluorinated electrolytes for Li-ion batteries. © 2021 American Chemical Society. All rights reserved.