The practical performances and thermal stability of Li-ion polymer batteries with LiNi0.8Co0.2O2, mesocarbon microbead-based graphite, and poly(acrylonitrile) (PAN)-based gel electrolytes are reported. The gel electrolyte, which shows a fire-retardance by itself as well as good chemical stability effectively improved thermal stability of the Li-ion polymer battery up to 170°C. We also found that the mesocarbon microbead-based graphite showed better coulombic efficiency even though the gel electrolyte contained PC and GBL. An evaluation of cell performances showed that the electrodes and the gel electrolyte were promising material for a next-generation Li-ion polymer battery.