Lithium primary cells have the advantages of stable operating voltage, high energy density, long storage life, low discharge rate, and wide operating temperature range. Although not as reusable as lithium ion batteries, lithium primary batteries have been used in various fields, such as medical, environmental, and military, which require a small amount of current for a lengthy period or combined safety. In this study, MnO₂/CF_x hybrid primary batteries comprising manganese dioxide and carbon fluoride (CF_x), the main cathode materials of lithium primary battery, were fabricated and their discharge performance was measured. The discharge curve of the Li-MnO₂/CF_x cells was classified into the MnO₂ phase and the CF_x phase at low C-Rate. As the ratio of CF_x increases, the discharge capacity of the battery increases, but the rate characteristics decreases. Considering all parameters such as capacity, rate capability, and temperature, the optimum amount of CF_x doping was 70%. The mixing ratio of CF_x/MnO₂ hybrid cathode can remarkably control the electrochemical performances and this kind of mixing ratio is expected to improve the electrochemical performances.