Three-dimensional (3D) olivine LiMn0.8Fe0.2PO4 nanoflowers constructed by two-dimensional (2D) nanoflakes have been successfully synthesized through an easy liquid phase method. Hierarchical LiMn0.8Fe0.2PO4/C could be easily formed via a liquid coating technology and subsequent calcination treatment. When acting as cathode materials for lithium ion batteries, the LiMn0.8Fe0.2PO4/C nanoflowers show excellent rate performance and cycle stability. The unique flower-like hierarchical structured LiMn0.8Fe0.2PO4 and thin carbon coating outside make this composite a promising candidate as cathode materials for lithium ion batteries.