Lithium metal capacitor (LMC), incorporating a redox-type lithium metal anode and a capacitive-type carbon cathode, delivers a combination of high energy and power characteristics, which is regarded as a promising electrochemical energy storage system. However, the unstable interface stability of lithium anode and the unclear capacitive mechanism of carbon cathode seriously restrict the advancement of LMC. Herein, an all-fluorinated electrolyte with high voltage stability has been designed for engineering 5 V LMC. It is noticed that a high-quality LiF-rich solid electrolyte interphase derived from all-fluorinated electrolyte effectively improves the interfacial stability of lithium metal anode, boosting the reversible Li plating/stripping behavior and suppressing dendrite growth. Moreover, analyzed by the thermodynamic perspective, the stable PF6−(FEC)2(FEMC)4 configuration with the lowest solvation energy mainly exists in the all-fluorinated electrolyte, which reveals that the suitable pore size distribution (1.3–4.6 nm) can ensure the strong adsorption/desorption process. Endowed by the all-fluorinated electrolyte, the established 5 V LMC paired with an optimized porous carbon sheet cathode manifests excellent electrochemical performances with an ultrahigh energy density of 537.6 Wh kgcathode−1 and a large power density of 17500 W kgcathode−1. This elaborate work affords in-depth insights based on fluorinated electrolyte strategy into the fabrication guidance of LMC.