MXene possesses high conductivity, excellent hydrophilicity, rich surface chemistry, hence holds great potential in various applications. However, MXene materials have low surface area utilization due to the agglomeration of ultrathin nanosheets. Assembling 2D MXene nanosheets into 3D multi‐level architectures is an effective way to circumvent this issue. Incorporation of MXene with other nanomaterials during the assembly process could rationally tune and tailor the specific surface area, porosity and surface chemistry of the MXene assemblies. The complementary and synergistic effect between MXene and nanomaterials could expand their advantages and make up for their disadvantages, thus boost the performance of 3D porous MXene composites. Herein, we summarize the recent progress in fabrication of porous MXene architectures from 2D to 3D, and also discuss the potential applications of MXene nanostructures in energy harvesting systems, sensing, electromagnetic interference shielding, water purification and photocatalysis.