The Na3V2(PO4)2O2F (NVPOF) is synthesized with high conversion rates and uniform morphology, by rapid precipitation of adjusting the pH and temperature. And the effect of reaction temperature on the performance is mainly investigated, and the results show that the rise of reaction temperature is beneficial to the increase of F content and conversion rate. Furthermore, micro morphology can be designed by adjusting temperature and other conditions. Then the NVPOF/C with modification of robust carbon coating is conducted, and the surface structure has been characterized. The optimized NVPOF/C based hybrid exhibits a specific capacity of 116.7 mAh·g−1 at 0.1C and it has long cycle performance (92.0 % retention rate after 200 cycles at 1C) and high capacity at high current density (78 mAh·g−1 at 10C). Consequently, a simple and controllable precipitation method is provided to prepare micro-nano NVPOF/C with high rate performance and indicate the importance of morphology and surface stability control.