Hierarchical LiFePO4 microflowers have been successfully synthesized via a solvothermal reaction in ethanol solvent with the self-prepared ammonium iron phosphate rectangular nanoplates as a precursor, which is obtained by a simple water evaporation method beforehand. The hierarchical LiFePO4 microflowers are self-assemblies of a number of stacked rectangular nanoplates with length of 6–8μm, width of 1–2μm and thickness of around 50nm. When ethanol is replaced with the water–ethanol mixed solvent in the solvothermal reaction, LiFePO4 micro-octahedrons instead of hierarchical microflowers can be prepared. Then both of them are respectively modified with carbon coating through a post-heat treatment and their morphologies are retained. As a cathode material for rechargeable lithium ion batteries, the carbon-coated hierarchical LiFePO4 microflowers deliver high initial discharge capacity (162mAhg−1 at 0.1C), excellent high-rate discharge capability (101mAhg−1 at 10C), and cycling stability, which exhibits better electrochemical performances than carbon-coated LiFePO4 micro-octahedrons. These enhanced electrochemical properties can be attributed to the hierarchical micro/nanostructures, which can take advantage of structure stability of micromaterials for long-term cycling. Furthermore the rectangular nanoplates as the building blocks can improve the electrochemical reaction kinetics and finally promote the rate performance.