Transition metal cation ordering is essential for controlling the electrochemical performance of cubic spinel LiNi0.5Mn1.5O4 (LNMO),which is conventionally adjusted by optimizing the high temperature sin-tering and annealing procedures.In this present work,multiple characterization techniques,including 6,7Li NMR,XRD and HRTEM,have been combined to trace the phase transformation and morphology evo-lution during synthesis.It has been illustrated that simultaneous formation of LiMn2O4 (LMO) and LiNiO2(LNO) binary oxides and their conversion into highly reactive LixNi3+yMn3.5+zO ternary intermediate is a thermal dynamically difficult but crucial step in the synthesis of LNMO ternary oxide.A new strategy of modifying the intermediates formation pathway from binary mode to ternary mode using thermal reg-ulating agent has been adopted.LNMO synthesized with thermal regulating agent exhibits supreme rate capability,long-cycling performance (even at elevated temperature) and excellent capacity efficiency.At a high rate of 100 C,the assembled battery delivers a discharge capacity of 99 mAh g-1.This study pro-vides a way to control the formation pathway of complex oxides using thermal regulating agent.