Mn-based Mn2O3 anode and LiMn2O4 cathode materials are prepared by a solvothermal method combined with post annealing process. Environmentally friendly ionic liquid 1-Butyl-3-methylimidazolium tetrafluoroborate as both structure-directing agent and fluorine source is used to prepare hollow polyhedron MnF2 precursor. Both target materials Mn2O3 anode and LiMn2O4 cathode have the morphology of the MnF2 precursor. The Mn2O3 anode using carboxymethyl cellulose as binder could deliver slight better electrochemical performance than the one using poly (vinyldifluoride) as binder. The former has an initial charge capacity of 800 mAh g−1 at a current density of 101.8 mA g−1, and exhibits no obvious capacity decay for 150 cycles at 101.8 mA g−1. The LiMn2O4 cathode material prepared with molten salt assistant could display much better electrochemical performance than the one prepared without molten salt assistance. In particular, it has an initial discharge capacity of 117.5 mAh g−1 at a current density of 0.5C and good rate capability. In the field of lithium ion batteries, both the Mn2O3 anode and LiMn2O4 cathode materials could exhibit enhanced electrochemical performance due to the well formed morphology based on the ionic liquid-assisted solvothermal method.