Electrolyte additives are necessary for the application of high potential cathode in high energy density lithium ion batteries, especially at elevated temperature. However, the electrolyte additives that can effectively suppress the dissolution of transition metal ions from cathode have seldom been developed up to date. In this work, we propose a novel electrolyte additive, trimethylsilylcyclopentadiene (SE), for high temperature application of a representative high potential cathode, lithium nickel manganese oxide (LiNi0.5Mn1.5O4). It is found that the dissolution of Mn and Ni from LiNi0.5Mn1.5O4 can be effectively suppressed by applying SE. With applying 0.25% SE, the dissolved amount of Mn and Ni is decreased by 97.4% and 98%, respectively, after 100 cycles at 55 °C. Correspondingly, the cyclic performance of LiNi0.5Mn1.5O4 is significantly improved. Physical characterizations and electrochemical measurements show that SE can be preferentially oxidized and generate a protective film on LiNi0.5Mn1.5O4. The resulting film inhibits the electrolyte decomposition and the transition metal ion dissolution.