In this study, the cross-linking-type gel polymer electrolyte (GPE) was prepared using trimethylolpropane triacrylate and trimethylolpropane ethoxylate triacrylate and their electrochemical performances were evaluated. The ionic conductivity of the GPE at 20°C was around 5 × 10−3 ∼ 6 × 10−3 Scm−1. The GPE had good electrochemical stability up to 4.5V versus Li/Li+. The electrochemical performance of TMPETA-based cell was better than that of TMPTA-based cell. The discharge capacity of the TMPETA-based cell at the 2.0C rate was 98% of the discharge capacity at the 0.2C rate. The discharge capacity of the TMPTA- and TMPETA-based cell was stable with the charge–discharge cycling