We report synthesis of lithium poly (4-vinylphenol) phenolate borate (LiPVPPB) single-ion conductor comprised of boron atoms with sp3 electronic configuration covalently bonded to a polystyrene backbone with high thermal and electrochemical stability. The highly delocalized anionic charges surrounding the boron atoms in the polymer give rise to weak association with lithium ions in the polymer matrix, resulting in an ion transference number close to unity and remarkably high ionic conductivity. A composite membrane blended with LiPVPPB and poly(vinylidene-fluoride-co-hexafluoropropene) (PVDF-HFP) was fabricated. The battery of the electrolyte displays excellent cyclability with nearly 100% coulombic efficiency over a wide temperature range. The superior membrane performance suggests that single ion polymer electrolyte materials are highly promising for safe and high power applications of lithium ion batteries.