Localized　high-concentration　electrolytes　(LHCEs)　offer　a　new　methodology　to　improve　the　functionality　of　conventional　electrolytes.　Understanding　the　impact　of　antisolvents　on　bulk　electrolytes　is　critical　to　the　construction　of　sophisticated　LHCEs.　However,　the　mechanism　of　how　antisolvent　modulates　the　electrochemical　reactivity　of　the　solvation　structure　in　LHCEs　remains　unclear.　In　this　work,　the　key　correlation　between　the　physicochemical　properties　of　antisolvents　and　their　corresponding　Lithium-ion　battery　(LIBs)　systems　has　been　elucidated　by　comprehensive　multiscale　theoretical　simulations　combined　with　experimental　characterizations.　Nine　antisolvents　(chain　ethers　and　cyclic　non-ethers)　are　investigated　in　a　typical　lithium　bis(fluorosulfonyl)　imide/1,2-dimethoxymethane　(LiFSI/DME)　system.　It　is　highlighted　that　the　relative　molecular　masses　of　anti-　solvents　in　the　same　class　are　positively　correlated　with　the　density.　The　viscosity　of　a　liquid　mixture　consisting　of　DME　and　antisolvent　in　the　same　class　is　positively　correlated　with　the　magnitude　of　the　interaction　energy　between　them.　Additionally,　the　self-diffusion　coefficient　of　Li+　is　also　positively　correlated　with　the　sum　of　the　interaction　energies　between　Li+-DME　and　Li+-FSI-,　which　is　also　affected　by　the　class　of　antisolvent.　These　results　provide　deep　insights　into　the　behavior　and　properties　of　LHCEs,　which　help　to　advance　the　design　of　high-performance　LIBs.