This article reports the development of a new dicarbonate-based electrolyte for 5 V-class lithium-based batteries, which uses dimethyl 2,5-dioxahexanedioate (DMDOHD) as the solvent. The DMDOHD-based electrolyte exhibits superior anodic stability up to 5.2 V (vs. Li/Li+) and enables stable, dendrite-free lithium plating and stripping. The electrolyte also shows high lithium plating/stripping coulombic efficiency (CE) of 92% without additives or co-solvents, and excellent cycling stability with a capacity retention of >97% after 250 cycles in Li | LiNi0.5Mn0.5O4 cells. The improved performance is attributed to the formation of a robust solid-electrolyte interphase (SEI) with homogeneous inorganic-organic mixed components and a dense cathode-electrolyte interphase (CEI). The addition of fluoroethylene carbonate (FEC) further enhances the lithium plating/stripping CE and capacity retention. The study demonstrates the potential of dicarbonate solvents, particularly DMDOHD, for high-voltage lithium-based batteries, offering a promising approach to achieve higher energy density and improved safety.This article reports the development of a new dicarbonate-based electrolyte for 5 V-class lithium-based batteries, which uses dimethyl 2,5-dioxahexanedioate (DMDOHD) as the solvent. The DMDOHD-based electrolyte exhibits superior anodic stability up to 5.2 V (vs. Li/Li+) and enables stable, dendrite-free lithium plating and stripping. The electrolyte also shows high lithium plating/stripping coulombic efficiency (CE) of 92% without additives or co-solvents, and excellent cycling stability with a capacity retention of >97% after 250 cycles in Li | LiNi0.5Mn0.5O4 cells. The improved performance is attributed to the formation of a robust solid-electrolyte interphase (SEI) with homogeneous inorganic-organic mixed components and a dense cathode-electrolyte interphase (CEI). The addition of fluoroethylene carbonate (FEC) further enhances the lithium plating/stripping CE and capacity retention. The study demonstrates the potential of dicarbonate solvents, particularly DMDOHD, for high-voltage lithium-based batteries, offering a promising approach to achieve higher energy density and improved safety.