In this study, a strategy for synthesizing lithium methacrylate (LiMA)-based self-doped gel polymer electrolytes was described and the electrochemical properties were investigated by impedance spectroscopy and linear sweep voltammetry. LiMA was found to dissolve in ethylene carbonate (EC)/diethyl carbonate (DEC) (3/7, v/v) solvent after complexing with boron trifluoride (BF3). This was achieved by lowering the ionic interactions between the methacrylic anion and lithium cation. As a result, gel polymer electrolytes consisting of BF3–LiMA complexes and poly(ethylene glycol) diacrylate were successfully synthesized by radical polymerization in an EC/DEC liquid electrolyte. The FT-IR and AC impedance measurements revealed that the incorporation of BF3 into the gel polymer electrolytes increases the solubility of LiMA and the ionic conductivity by enhancing the ion disassociations. Despite the self-doped nature of the LiMA salt, an ionic conductivity value of 3.0×10−5 Scm−1 was achieved at 25°C in the gel polymer electrolyte with 49wt% of polymer content. Furthermore, linear sweep voltammetry measurements showed that the electrochemical stability of the gel polymer electrolyte was around 5.0V at 25°C.