A novel acrylol borate was designed and synthesized by reacting acrylate monomer and boric acid. The obtained acrylol borate was used as both gelator and anion receptor for the liquid electrolyte in a lithium secondary battery. It was found that the ionic conductivity of the gel polymer electrolyte (GPE) was as high as that of the liquid electrolyte, and the thermal stability of GPE was increased when only 2 wt% acrylol borate was incorporated into the liquid electrolyte. These results suggest that acrylol borate can be used as an effective additive to enhance the thermal stability of the electrolyte without adversely affecting its conductivity. It is believed that the strong complex formation between boron in the gelator and the anion of the salt is responsible for the enhanced thermal stability of the electrolyte solution and the increased ionic conductivity.