A facile and effective route was developed for the fabrication of LiFe0.2Mn1.8O4 with porous structures by using Pluronic P-123 as a soft template, based on a nitrate decomposition method. The resultant LiFe0.2Mn1.8O4 was characterized by XRD, SEM, as well as N2 adsorption/desorption measurements which showed a porous structure with a pore size centered at 20nm. When used as cathode materials in lithium battery, the as-synthesized LiFe0.2Mn1.8O4 exhibited a discharge capacity of 122mAhg−1 at 1C and 102mAhg−1 at 5C. Moreover, after 500 cycles, the capacity retention (108mAhg−1) reached 88% of the initial capacity at 1C. As compared with conventional cathode LiMn2O4, the high performance is believed to originate from the combined effects of porous structure, iron doping and highly crystalline nature of the obtained LiFe0.2Mn1.8O4. This strategy is expected to allow the fabrication of other multiple metal oxides with porous structures for high performance cathode materials.