A lithium iron phosphate hierarchical structure includes a plurality of lithium iron phosphate nano sheets and has an overall spherical-shaped structure. The overall spherical-shaped structure is constructed by a plurality of lithium iron phosphate nano sheets layered together. A method for making a lithium iron phosphate hierarchical structure includes several steps. In the method, a lithium ion contained liquid solution, a ferrous ion contained liquid solution, and a phosphate ion contained liquid solution are respectively provided. A concentration of lithium ions in the lithium ion contained liquid solution is equal to or larger than 1.8 mol/L. The lithium ion contained liquid solution, the ferrous ion contained liquid solution, and the phosphate ion contained liquid solution are mixed to form a liquid mixture. The liquid mixture is heated in a sealed reactor to form the lithium iron phosphate hierarchical structure.