Structural and transport properties of a newly designed high-transference number electrolyte (HTNE) system consisting of perfluoropolyether-block-poly(ethylene oxide) (PFPE-PEO; PFPEE10-Diol) as the solvent in a mixture with the lithium salt bis(trifluoromethanesulfonyl)imide (LiTFSI) for application in lithium-ion batteries (LIBs) are studied by molecular dynamics (MD) simulation. The obtained results indicate a correlation between the transference number (t +) and ionic conductivity (σ) of Li+. Therefore, an effective ionic conductivity parameter (σt +) is introduced to treat the transport properties of the electrolyte system. Analysis of the results leads to the conclusion that at a high temperature (423 K) and a salt (LiTFSI) concentration of 0.89 M, the studied HTNE system (PFPEE10) would show the highest performance, especially more efficient charge transfer, if employed as an electrolyte, in the LIB operation.