Herein, we report on a novel precipitation method to enable LiMnPO4 olivine (LMP) as a cathode material for lithium ion batteries (LIBs) to reach high capacity at high discharge rates. By confining Mn3(PO4)2 precipitation on surface of a precursor seed of Li3PO4, the size of LMP particles is limited to less than 100nm for a smaller dimension. The cathode material delivers discharge capacities of 145mAhg−1 at 0.1C, 112mAhg−1 at 1C to 62mAhg−1 at 5C (comparable with top three performances [1–3]). Even if precipitation is one of the versatile strategies to prepare the cathode material, it has not been reported that such a first-tier high performance is obtained from LMP prepared by precipitation methods. When compared with LMP particles synthesized by a conventional co-precipitation method, the performances are recognized to be considerably enhanced. Also, the surface-confined precipitation process described in this work does not involve a ball milling step with a conductive agent such as carbon black [1,2,4–10] so that a low cost synthesis is feasible.