MXenes are a family of two-dimensional (2D) materials with interesting electrical and electrochemical properties and their high potential as electrode materials for Li-ion capacitors has been recently demonstrated. However, the conventional methods for electrode assembly and device fabrication are limiting factors in exploiting the full potential of these electrode materials. The research on the development of electrochemical energy storage devices in the past few years has led to the realization that improved performance can be achieved by assembling the electrode materials into three-dimensional (3D) architectures instead of the conventional 2D “laminate” architecture. In this talk, we present a simple, efficient, and scalable method to assemble 2D Ti3C2 into ordered 3D and porous aerogel structures with high specific capacitances and rate capabilities. MXenes aerogels are fabricated by directional freeze casting and show large specific surface areas. The porous structure of MXene aerogels is dependent on the processing conditions and affect their mechanical and electrochemical properties. MXene aerogels show significantly high specific capacities (1200 mAh/g at 0.05 A/g), excellent rate capability (200 mAh/g at 10 A/g) and outstanding cycling performance for reversible lithium-ion energy storage. We believe that the fabricated 3D MXene structures are promising for a broad range of applications.