In this study, we have investigated N-phenylmaleimide/bismaleimide- containing branched oligomer (BO1) as additive in Li-ion batteries to increase the safety performance by reducing the probability of batteries suffering an internal short circuit. In the nail penetration test, a LiCoO 2 /MCMB full battery with N-phenylmaleimide/bismaleimide-containing branched oligomer (BO1) showed a significant improvement in thermal stability and was able to restrain the temperature of the battery at about 85 °C. Furthermore, we found that N-phenylmaleimide/bismaleimide-containing branched oligomer (BO1) contained battery revealed better cycling and electrochemical performance, compared with the battery with bismaleimide-containing branched oligomer (BO3) in the electrolyte. The improvement might result from the favorable ionic conductivity, Li ion mobility and lower resistance in the battery. This additive can meet the cycling performance and safety requirements for Li-ion batteries.