P2-type Na2/3Fe1/2Mn1/2O2 cathode material is synthesized by a modified solid-state method with organic metal salts as raw materials, which can reduce the temperature and time of heat treatment, and highly enhance the electrochemical performance. XRD results indicate that the sample is a pure P2-type Na2/3Fe1/2Mn1/2O2 phase with well-developed crystal structure. Furthermore, a regular hexagon plate shape for the uniformly distributed particles is revealed by SEM and TEM results. The mean size and thickness of the hexagon plates are about 1–4µm and 200–700nm, respectively. The P2-Na2/3Fe1/2Mn1/2O2 sample synthesized at 800°C for 8h exhibits the initial specific discharge capacities of 230.0 and 111.4mAhg−1 at 0.1C and 2C rates, respectively, and after 130 cycles, the sample still exhibits good performance.