This study systematically investigates the control mechanisms of electron density (ne) and electron temperature (Te) in 13.56 MHz capacitively coupled CF4/Ar plasmas using Langmuir probe diagnostics. Experiments reveal that ne increases with chamber pressure (negligibly above 50% CF4), peaks at 5–10% CF4 content due to enhanced Penning ionization, and rises with discharge power before saturating above 200 W. Conversely, Te decreases with pressure due to heightened collisional energy losses, increases monotonically with CF4 concentration via electronegativity-enhanced sheath heating, and exhibits power-dependent divergence: decreasing at low CF4 (≤50%) from energy dilution and collisional dissipation, but slightly increasing at high CF4 (≥80%) due to suppressed electron density and reduced energy losses. Parameter-specific adjustments are identified: (1) Pressure elevation boosts ionization in Ar-dominated plasmas but enhances electron attachment in CF4-rich environments; (2) Low CF4 addition (≤10%) optimizes ne through Penning effects, while higher CF4 promotes dissociative recombination; (3) Power increase initially enhances ionization but induces Te reduction in electronegative regimes except in CF4-dominated systems where low electron density limits energy dissipation. These findings establish synergistic tuning strategies for plasma etching processes through coordinated control of pressure, gas ratio, and power.