Mesoporous FeF3(H2O)(0.33) microspheres, hexagonal columns, and beta-FeF3 center dot 3H(2)O 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 (159.2 mA h g(-1) at 142 mA g(-1) after 100 cycles). Even at a high current density of 474 mA g(-1), mesoporous FeF3(H2O)(0.33) microspheres still deliver a discharge capacity as large as 95.9 mA h g(-1) after 100 cycles. This remarkable electrochemical performance can be attributed to the high specific surface area and mesoporous microspherical 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. (C) 2014 Elsevier Ltd. All rights reserved.