Recently, the spray drying technology has emerged as an effective approach in preparing battery materials due to its advantage of preparing spherical particles with excellent dispersion, [27][28][29] which typically includes atomizing the raw material slurry and dry it into spherical particles with the excellent dispersing ability through high-temperature heat flow. However, the obtained sphere typically exhibits hollow interior with low tap density and specific surface area. The inner surface is hard to contact the electrolyte effectively, resulting in the poor electrochemical performance of active material.There are several reports on the preparation of fluorine-containing cathode materials such as LiVPO 4 F and Na 3 V 2 (PO 4 ) 2 F 3 through the spray drying method. Ding et al. [30] and Sui et al. [31] prepared pure phase LiVPO 4 F with excellent electrochemical performance through a two-step spray drying method. However, it is difficult to accurately match the addition amount of LiF due to the loss of VPO 4 in the spray drying process, and the energy consuming is large. Eshraghi et al. [32] and Shen et al. [33] have successfully synthesized spherical particles of Na 3 V 2 (PO 4 ) 2 F 3 by adding excessive NaF in one-step spray drying method. However, the excessive introduction of sodium element results in the formation of inert sodium salt, which is detrimental to the electrochemical performance of Na 3 V 2 (PO 4 ) 2 F 3 /C cathode. The utilization of high-energy ball milling also destroys the spherical structure and increases the production costs.Both the two-step method and the excessive addition of NaF were used to inhibit the production of impurity. For Na 3 V 2 (PO 4 ) 2 F 3 , the loss of fluorine during the synthesis process leads to the formation of Na 3 V 2 (PO 4 ) 3 , which is also a sodium superionic conductor and possesses only one voltage plateau at 3.4 V with theoretical capacity of 117.6 mAh g −1 . However, low voltage plateau and theoretical capacity lead to low energy density. In comparison, Na 3 V 2 (PO 4 ) 2 F 3 with an average voltage of 3.9 V and theoretical capacity of 128.4 mAh g −1 exhibit a promising application value.In this work, we have successfully synthesized pure phase porous spherical Br-doped Na 3 V 2 (PO 4 ) 2 F 3 particles by a simple one-step spray drying method. The hard template fluoropolymer polytetrafluoroethylene (PTFE) and soft template surfactant cetyltrimethylammonium bromide (CTAB) were utilized as the supplement and regulative agent of fluorine in the synthesis process of Na 3 V 2 (PO 4 ) 2 F 3 /C, respectively. Their influences on the structure, morphology, and electrochemical performance of Na 3 V 2 (PO 4 ) 2 F 3 /C were also investigated systematically. The density functional theory (DFT) calculation was further used to analyze the doping effect of Br on the density of states (DOS) and the diffusion barriers of Na ions.