Abstract Organic hybrid supercapacitors that consist of a battery electrode and a capacitive electrode show greatly improved energy density, but their power density is generally limited by the poor rate capability of battery‐type electrodes. In addition, flexible organic hybrid supercapacitors are rarely reported. To address the above issues, herein an in‐plane assembled orthorhombic Nb 2 O 5 nanorod film anode with high‐rate Li + intercalation to develop a flexible Li‐ion hybrid capacitor (LIC) is reported. The binder‐/additive‐free film exhibits excellent rate capability (≈73% capacity retention with the rate increased from 0.5 to 20 C) and good cycling stability (&gt;2500 times). Kinetic analyses reveal that the high rate performance is mainly attributed to the excellent in‐plane assembly of interconnected single‐crystalline Nb 2 O 5 nanorods on the current collector, ensuring fast electron transport, facile Li‐ion migration in the porous film, and greatly reduced ion‐diffusion length. Using such a Nb 2 O 5 film as anode and commercial activated carbon as cathode, a flexible LIC is designed. It delivers both high gravimetric and high volumetric energy/power densities (≈95.55 Wh kg −1 /5350.9 W kg −1 ; 6.7 mW h cm −3 /374.63 mW cm −3 ), surpassing previous typical Li‐intercalation electrode‐based LICs. Furthermore, this LIC device still keeps good electrochemical attributes even under serious bending states (30°–180°).

In‐Plane Assembled Orthorhombic Nb2O5 Nanorod Films with High‐Rate Li+ Intercalation for High‐Performance Flexible Li‐Ion Capacitors