In order to combine the advantages of both traditional gel electrolytes and polyelectrolytes, a novel polyelectrolyte which incorporates a boroxine ring-containing anion-trapping agent has been explored. Poly(lithium 2-acrylamido-2-methyl-1-propanesulfonate) (PAMPSLi), ethylene carbonate (EC) and tri(methoxyethoxyethoxyethoxy)boroxine (TME3Bx) were combined to prepare various gel systems. The thermal properties and conductivities of these gels have been investigated. A conductivity of 10−3.6 S cm−1 at 20 °C has been achieved in a gel polyelectrolyte system with a molar ratio of [EC]:[TME3Bx]:[Li+]=24:1.7:1. Temperature-dependent NMR measurements indicated that a significant interaction exists between the boroxine ring and the polyelectrolyte.