Ti3C2T x MXene is a promising material for electrodes in microsupercapacitors. Recent efforts have been made to fabricate MXene electrodes with designed structures using 3D printing to promote electrolyte permeation and ion diffusion. However, challenges remain in structural design diversity due to the strict ink rheology requirement and limited structure choices caused by existing extrusion-based 3D printing. Herein, additive-free 3D architected MXene aerogels are fabricated via a 3D printed template-assisted method that combines 3D printed hollow template and cation-induced gelation process. This method allows the use of MXene ink with a wide range of concentrations (5 to 150 mg mL–1) to produce MXene aerogels with high structural freedom, fine feature size (>50 μm), and controllable density (3 to 140 mg cm–3). Through structure optimization, the 3D MXene aerogel shows high areal capacitance of 7.5 F cm–2 at 0.5 mA cm–2 with a high mass loading of 54.1 mg cm–2. It also exhibits an ultrahigh areal energy density of 0.38 mWh cm–2 at a power density of 0.66 mW cm–2.

The assembly of different levels of structure from the nano‐ to the macroscale has produced materials with outstanding performance. Here, using graphene as a model building block, the fabrication of multiscale structures is reported, with tailorable features spanning seven orders of magnitude in size by a 3D printed template‐directed assembly method which combines the ability to customize structures from the meso‐ to macroscale using digital light processing and from the nano‐ to microscale using self‐assembly. It is shown that by a careful design of the structures, a number of extraordinary properties can be produced including ultralow density (≥0.08 mg cm–3), and ultrahigh stiffness, and compressibility (full recovery from 95% strain). The approach not only provides diversified structure control over wide length scales for nanomaterial assembly but also shows the possibility of changing the properties of the structure for different applications.