Supercapacitors (SCs) are important energy storage devices that are increasingly playing an important role in various applications. [1-6] Though SCs can offer high power density, they have lower energy density in comparison to batteries. [1] The high power density makes them suitable for applications such as uninterruptible power supply (UPS), portable tools, rubber-tired gantry crane, and emergency doors on airplanes. [1,2] However, in order to deploy SCs in automotive and grid storage applications, their energy density needs to be significantly uplifted. [7,8] To enhance the energy density of SCs, which is calculated using this equation (E = 0.5 C V 2), either the specific capacitance (C) or cell voltage (V) needs to be improved. [2,9] The C values of the SC device can be improved by tuning the intrinsic properties of the electrode material. [10] For example, employing pseudocapacitive electrode materials is an effective strategy to enhance the specific capacitance (C) of the SC. [8] Pseudocapacitive materials, in general, show high capacitance values in comparison to electrical double layer capacitor (EDLC) based materials due to their fast reversible electron transfer redox reactions. [8] On the other hand, the cell voltage (V), the second major factor which influences the energy density, is greatly controlled by device engineering. [8,11] Organic electrolyte based SC devices usually offer a higher voltage window in comparison to aqueous devices. [8,11] However, the former suffers from some disadvantages such as low ionic mobility, high cost, toxicity, and not being environmentally benign. [12] On the other hand, aqueous electrolyte based SCs go without the aforementioned disadvantages, but the conventional symmetric SCs with aqueous electrolyte are hampered by low voltage windows. [12] In case of aqueous electrolyte SCs, the voltage window can be significantly improved by constructing asymmetric supercapacitors (ASCs). [12,13] In ASCs, two different electrode materials are used separately for the negative and positive electrodes. [12,13] The complementary potential windows of the individual electrodes enable the ASC device to cross the thermodynamic break New covalent organic frameworks (COFs), encompassing redox-functionalized moieties and an aza-fused π-conjugated system, are designed, synthesized, and deployed as negative electrodes in asymmetric supercapacitors (ASC), for the first time. The Hex-Aza-COFs are synthesized based on the solvothermal condensation reaction of cyclohexanehexone and redox-functionalized aromatic tetramines with benzoquinone (Hex-Aza-COF-2) or phenazine (Hex-Aza-COF-3). The redox-functionalized Hex-Aza-COFs show a specific capacitance of 585 F g −1 for Hex-Aza-COF-2 and 663 F g −1 for Hex-Aza-COF-3 in a three-electrode configuration. These values are the highest among reported COF materials and are comparable with state-of-the-art pseudocapacitive electrodes. The Hex-Aza-COFs exhibit a wide voltage window (0 to −1.0 V), which allow the construction of a two-electrode ASC device b...