Na3V2(PO[Formula: see text] (NVP) as one typical Na[Formula: see text] super ionic conductor (NASICON) is recognized as an ideal cathode material for ZIBs owing to its promising structural stability that facilitates long cycle, rich vacancies and channels facilitate storing metal ions, high operating potentials to ensure high energy density. However, it still faces poor cyclability and high-rate capacity. Here, three-dimensional networked Na3V2(PO[Formula: see text]/C composite is synthesized by a microemulsion strategy with cetyltrimethyl ammonium bromide (CTAB) as the soft template, and the effect of aging temperature of microemulsion on their morphology and electrochemical performance is investigated. The Na3V2(PO[Formula: see text]/C composite derived from the precursor reacted at 70[Formula: see text]C shows micrometer-size particles assembled by three-dimensional networked nanoplates, facilitating for ions transport and delivers the best electrochemical performance. It displays a high first capacity of 102.2 mAh g[Formula: see text] with 42.3 mAh g[Formula: see text] remained after 5000 stable cycles (capacity retention of 41.4%) at 5 C, a high capacity of 83.2 mAh g[Formula: see text] even the current density is as high as 20 C, which is better than most of the reports.