The advancement of the modern world demands high‐performance electrical energy storage devices such as metal‐ion capacitors and dual‐ion batteries, and they receive much attention recently with the merits of cost‐effectiveness, safety, environmental friendliness, and high operating voltage. This work emphasizes the metal‐ion capacitors (Li+, Na+, and K+) based on the dual‐carbon combination in which anion intercalation endorses the Faradaic reaction and cation involves in the non‐Faradaic process, promising for greater energy density. The role of graphite, anion graphite intercalation compounds, and the information about the megalo‐capacitance capacitor are first discussed. Subsequently, various influencing factors such as the effect of solvent, electrolyte, conducting salt, cations, and anions affecting the intercalation process are debated in detail. In addition, recently emerging various metal‐ion capacitors based on the anion intercalation process are also reviewed. The major challenges present in the development of the anion‐based hybrid capacitor are finally evaluated and an assessment to fulfill the goals for efficient energy storage is provided.

Supercapacitors are characterized by their fast charge/discharge capability, high‐power capability, and long cycle life, but low‐energy‐density impedes their practical application. The requirement of achieving a highly efficient energy storage system demands the hybridization of supercapacitors and batteries. The anion‐intercalation chemistry of graphite with high insertion potential creates a possibility of using graphite as a cathode, which works as an acceptor‐type graphite intercalation compound. Herein, we report the reversible PF6– anion storage on the graphite cathode, which occurs by the combination of pseudocapacitive and diffusion‐limited redox reaction at a higher working potential. Furthermore, a dual carbon lithium‐ion capacitor (LIC) using commercial graphite as anion‐intercalation type, battery type cathode, and commercial‐activated carbon (AC) as supercapacitor type anode is designed. The assembled preanion intercalated Graphite/AC‐based LIC assembly displayed a high‐energy density of 90.73 Wh kg–1. Moreover, the device with low‐temperature stability is advantageous over traditional electrical double‐layer capacitors, mainly in terms of its energy and low cost with much more safety features than commercial lithium‐ion batteries.