Poly(ethylene glycol) borate acrylate (PEGBA) was synthesized as a new crosslinking agent for solid polymer electrolyte (SPE) based on non-woven matrix. It has not only three crosslinkable acrylate groups for higher crosslinking density, but also Lewis acid center acting as an anion receptor. The ionic conductivity of SPE containing 15 wt.% PEGBA reached 5.5 × 10−4 S cm−1, because the content of non-volatile plasticizer, poly(ethylene glycol) dimethyl ether (PEGDME), could be increased to 85 wt.% without leakage. In addition, its transference number and electrochemical stability were also enhanced to 0.37 and 5.2 V, respectively, due to the presence of Lewis acid center in PEGBA.