Here, we prepared LiMn0.8Fe0.2PO4 microspheres with an open three-dimensional nanoporous structure by a facile ion-exchange solvothermal method. The micro/nano-structured material exhibits an ultralong cycle life, and retains a reversible capacity of 105 mA h g(-1) after 1000 cycles at 5 C, corresponding to the capacity retention of 94.0% and only 0.0068 mA h g(-1) loss per cycle.