The low intrinsic conductivity of carbon monofluoride (CFx) extremely limits the high-power application of lithium/carbon monofluoride (Li/CFx) primary batteries. Herein, silver nanowires were grown in situ on the surface of CFx material by an aldehyde reduction method in polyhydric alcohol. The interface interaction between silver nanowires (Ag NWs) and the surface of CFx material was studied. Ag NWs@CFx hybrids modulate the electronic structure of CFx and enhance the electrochemical activity of C–F bonds, thus increasing the availability of F atoms to participate in the discharge reaction. The electrochemical performance results show that the voltage platform, specific capacity, and energy density of the Li/CFx batteries were enhanced with a certain concentration of Ag NWs on the CFx surface. The 10% Ag NWs@CFx sample achieved a power density of 10376.09 W/kg and an energy density of 840 Wh/Kg at a discharge rate of 8C, which is significantly better than the pristine CFx. The perfo