The theoretical energy density of lithium/fluorinated carbon battery (Li/CFx) is as high as 2180 Wh·kg-1. However, due to the poor electrical conductivity and low vibrational density of the fluorinated carbon (CFx), there is a problem of low capacity utilization rate of the CFx materials in battery applications. Previous studies have shown that the physical properties and chemical properties such as particle size, specific surface area and degree of fluorination have a great influence on the electronic conductivity and capacity utilization of CFx. In this paper, based on the study of the microstructure, specific surface area and particle size of hierarchical CFx, novel composite hierarchical CFx were prepared by physical ball milling method. By adjusting the mass ratio of hierarchical CFx, the micro morphology, electrode structure and electrochemical mechanism of the novel composite CFx were studied, and the impedance and electrochemical performance of batteries with composite CFx as cathode material were further compared. The results show that the novel composite CFx reduces the porosity of the electrode, increases the contact tightness between the particles and effectively reduces the charge transfer resistance of the battery. The battery uses CF73 composite as cathode material, whose resistance decreases by 62% and specific energy increases by 4.1% compared with the battery using single CF01 as cathode material.