Abstract Constructing dual‐ion energy storage devices using anion‐intercalation graphite cathodes offers the unique opportunity to simultaneously achieve high energy density and output power density. However, a critical challenge remains in the lack of proper anodes that match with graphite cathodes, particularly in sustainable electrolyte systems using abundant potassium. Here, a surface grafting approach utilizing multifunctional azobenzene sulfonic acid is reported, which transforms V 2 C MXene into a high‐kinetics K + ‐intercalation anode (denoted ASA‐V 2 C) for dual‐ion energy storage devices. Importantly, the grafted azobenzene sulfonic acid offers extra K + ‐storage centers and fast K + ‐hopping sites, while concurrently acting as a buffer between V 2 C layers to mitigate the structural distortion during K + intercalation/de‐intercalation. These functionalities enable the V 2 C electrode with significantly enhanced specific capacity (173.9 mAh g −1 vs 121.5 mAh g −1 at 0.05 A g −1 ), rate capability (43.1% vs 12.0% at 20 A g −1 ), and cycling stability (80.3% vs 45.2% after 900 cycles at 0.05 A g −1 ). When coupled with an anion‐intercalation graphite cathode, the ASA‐V 2 C anode demonstrates its potential in a dual‐ion energy storage device. Notably, the device depicts a maximum energy density of 175 Wh kg −1 and a supercapacitor‐comparable power density of 6.5 kW kg −1 , outperforming recently reported Li + ‐, Na + ‐, and K + ‐based dual‐ion devices.