We demonstrate a rapid and one-pot solvothermal synthesis of LiFePO4 hierarchical nanorods and flowers like microstructures in a short reaction time (4–10min) at temperature as low as 300–400°C, without any high temperature post-annealing. The ethylene glycol was used as a solvent with hexane and oleic acid as co-solvent and surfactant, respectively. Addition of the co-solvent and/or surfactant played a key role in controlling the morphology and microstructures of the LiFePO4 nanocrystals. The EG and oleic acid were acted as the size and morphology controlling agents and carbon source when annealed at 600°C. Sample exhibited about 90% specific capacity at 0.5°C and showed good cyclic performance. The high-resolution TEM image revealed that these nanorods were self-assembled to form flower like microstructure in presence of oleic acid during the synthesis.