AbstractElectrolytic manganese dioxide is one of the promising cathode candidates for electrochemical energy storage devices due to its high redox capacity and ease of synthesis. Yet, high‐loading MnO₂ often suffers from sluggish reaction kinetics, especially in non‐aqueous electrolytes. The non‐uniform deposition of MnO₂ on a porous current collectors also makes it difficult to fully utilize the active materials at high mass loading. Here, a 3D printed graded graphene aerogel (3D GA) that contains sparsely separated exterior ligaments is developed to create large open channels for mass transport as well as densely arranged interior ligaments providing large ion‐accessible active surface. The unique structural design homogenizes the thickness of electro deposited MnO₂ even at an ultrahigh mass loading of ≈70 mg cm⁻². The electrode achieves a remarkable volumetric capacity of 29.1 mA h cm⁻³ in the non‐aqueous electrolyte. A Li‐ion hybrid capacitor device assembled with a graded 3D GA/MnO₂ cathode and graded 3D GA/VO_x anode exhibits a wide voltage window of 0–4 V and a superior volumetric energy density of 20.2 W h L⁻¹. The findings offer guidance on 3D printed electrode design for supporting ultrahigh loading of active materials and developments of high energy density energy storage devices.