Fluorinated carbons ( CFX) are promising cathode materials for lithium primary batteries due to their high energy density, yet suffer from poor electronic conductivity. Manganese dioxide ( MnO2), on the other hand, offers superior rate capability, but limited capacity. Here, we design MnO2/ CFx hybrid cathodes by combining MnO2 with CFX materials synthesized at controlled fluorination levels (x = 0.4–1.0) to synergistically optimize both energy and power performance. Structural and spectroscopic analyses reveal that moderate fluorination (x = 0.6) induces a favorable balance of semi-ionic C–F and interfacial O–F bonds, enhancing electron delocalization and charge transfer at the MnO2/ CFX interface. In contrast, excessive fluorination (x ≥ 0.8) leads to the formation of electrochemically inert C–F2 and C–F3 species, suppressing redox kinetics. As a result, MnO2/ CFX-0.6 delivers a discharge capacity of 390 mAh g–1−1 at 0.05 C and retains 182 mAh g–1−1 at 4 C, outperforming both pristine MnO2 and other CFX variants. This work establishes interfacial fluorine bonding configuration, not just bulk F/C ratio, as a critical design parameter for high-performance hybrid cathodes.