We present a tactful and advanced architecture design of self-supported, binder-free 3D hierarchical iron fluoride flower-like array directly growing on Ti foil by a solvothermal approach. The probable growth mechanism of the 3D microflower is explored. The advantages of the porous 3D hierarchical nanostructure materials endow a stable capacity of 123mAhg−1 at 3C rate, and a good rate capability of 101mAhg−1 at a high current density of 2Ag−1 (10C). The superior electrochemical performance can be ascribed to the synergistic effect of charge transfer expressway, high specific surface area and porous hierarchical structure for electrolyte penetration deriving from the unique porous 3D hierarchical structure. The superior electrochemical performance combined with the unique structure of the FeF3·0.33H2O flower-like array demonstrates its great potential of being utilized as the cathode material in high rate battery application.