Hollow sphere structure Na2MnPO4F/C composite is synthesized through spray drying, following in-situ pyrolytic carbon coating process. XRD results indicate that the well crystallized composite can be successfully synthesized, and no other impurity phases are detected. SEM and TEM results reveal that the Na2MnPO4F/C samples show intact hollow spherical architecture, and the hollow spherical shells with an average thickness of 150 nm–250 nm are composed of nanosized primary particles. Furthermore, the amorphous carbon layer is uniformly coated on the surface of the hollow sphere, and the nanosized Na2MnPO4F particles are well embedded in the carbon networks. Consequently, the hollow sphere structure Na2MnPO4F/C shows enhanced electrochemical performance. Especially, it is the first time that the obvious potential platforms (∼3.6 V) are observed during the charge and discharge process at room temperature.