In this work, a gel polymer electrolyte (GPE) was prepared using polyoxyalkylene glycol acrylate (POAGA) as a macromonomer. LiNi1/3Mn1/3Co1/3O2/GPE/graphite cells were prepared and their electrochemical properties were evaluated at various current densities and temperatures. The ionic conductivity of the GPE was more than 6.2×10−3 Scm−1 at room temperature. The GPE had good electrochemical stability up to 5.0V versus Li/Li+. POAGA-based cells were showed good electrochemical performances such as rate capability, low-temperature performance, and cycleability. No leakage of the electrolyte or an explosion was observed at the overcharge test.