A bicontinuous ordered network of 3D porous Na3(VO)2(PO4)2F/reduced graphene oxide (NVOPF/rGO) is prepared by a two‐step strategy (solvothermal plus electrostatic spray deposition method). Such electrodes exhibit excellent rate capability and cycling stability for both half cell and full cell, as well as a significant contribution of pseudocapacitance, resulting in real high power‐high energy sodium batteries. Abstract Developing high power‐high energy electrochemical energy storage systems is an ultimate goal in the energy storage field, which is even more difficult but significant for low‐cost sodium ion batteries. Here, fluoride is successfully prepared by the electrostatic spray deposition (ESD) technique, which greatly expands the application scope of ESD. A two‐step strategy (solvothermal plus ESD method) is proposed to construct a bicontinuous ordered network of 3D porous Na3(VO)2(PO4)2F/reduced graphene oxide (NVOPF/rGO). This two‐step strategy makes sure that NVOPF can be prepared by ESD, since it avoids the loss of F element during synthesis. The obtained NVOPF particles are as small as 15 nm, and the carbon content is only 3.5% in the final nanocomposite. Such a bicontinuous ordered network and small size of electroactive particles lead to the significant contribution of the pseudocapacitance effect to sodium storage, resulting in real high power‐high energy sodium cathodes. The cathode exhibits excellent rate capability and cycling stability, whose rate performance is one of the best ever reported in both half cells and full cells. Moreover, this work provides a general and promising strategy for developing high power‐high energy electrode materials for various electrochemical energy storage systems.

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