Here we report syntheses and study of composite solid polymer electrolytes (SPEs) based on a poly(ethylene glycol)-in-Li triflate material that contains an organic-inorganic composite (OIC) in which boron species are incorporated into a silica network. The structure and properties of the SPEs synthesized were characterized by scanning transmission electron microscopy (STEM), 29 Si, 11 B and 13 C solid state NMR, differential scanning calorimetry, and impedance spectroscopy. STEM allowed assessment of OIC particles in their native environment without removal of an organic component. The Lewis acid tricoordinate boron sites formed in OIC are proposed to have a stronger interaction with triflate anions than silica sites, which results in enhanced lithium ion conductivity and Li transference numbers at optimal boron concentrations. The optimum triethyl borate (TEB) concentration also leads to formation of smaller (higher surface area) OIC particles, which expose more boron sites to triflate anions. The SPE sample prepared with 10 mol% TEB exhibited a conductivity of 4.3 Â 10 À5 S cm À1 and a Li transference number of 0.89, which represents nearly single-ion conductor behaviour for the salt-in-polymer-borosilicate composite.