the electrochemical performance of LiFe0.75Mn0.25PO4 material is further enhanced via synergistic strategies including crystal orientation growth, microspherical self-assembly and graphene encapsulation. The crystal orientation growth of LiFe0.75Mn0.25PO4 with plate-like morphology not only reduces the Li-ion transport length, but also enlarges the (010) surface, and leads to the improvement of Li-ion diffusion. The self-assembled spherical hierarchical superstructures can effectively prevent the plane-plane stacks of LiFe0.75Mn0.25PO4 nanoplates during spontaneously aggregating, providing more (010) surface for Li+ insertion/extraction. The graphene encapsulation can build a 3D conductive network as well as stabilize the microspherical aggregations, resulting in superior electronic conductivity and stability. As a consequence of the synergistic effects, the as-obtained LiFe0.75Mn0.25PO4 sample exhibits excellent rate capability (141.1mAhg−1 at 5C, 126.5mAhg−1 at 10C, 107.7mAhg−1 at 20C) and outstanding cyclability (25°C, 94.6% capacity retention after 500 cycles at 1C). The synergistic strategy involving crystal orientation growth, microspherical self-assembly and graphene encapsulation provides a fascinating candidate to obtain superior olivine-type cathode materials with excellent rate capability and cycling stability, and holds the potential to be extended to the controlled preparation of other electrode materials.