Mesoporous FeF3(H2O)0.33 microspheres, hexagonal columns, and β-FeF3 ·3H2O square microrods have been prepared via facile solution methods using polyethylene glycol, oleic acid, and dodecyl trimethyl ammonium chloride as a surfactant, respectively. The as-prepared mesoporous FeF3(H2O)0.33 microspheres exhibits an enhanced lithium storage capacity and excellent cycling stability (159.2mAhg−1 at 142mAg−1 after 100 cycles). Even at a high current density of 474mAg−1, mesoporous FeF3(H2O)0.33 microspheres still deliver a discharge capacity as large as 95.9mAhg−1 after 100 cycles. This remarkable electrochemical performance can be attributed to the high specific surface area and mesoporous micro-spherical structure, which effectively increase the contact area between the active materials and the electrolyte, reducing the Li-ion diffusion pathway and buffering the volume change during cycling.