Transition metal carbides (MXenes) are novel two‐dimensional (2D) nanomaterials with exceptional properties, promising significant impact in applications such as energy storage and conversion, and catalysis. A major barrier preventing the widespread use of MXenes is the lack of methods for assembling MXene in 3D space without restacking, which degrades their performance. Here, we successfully overcome this challenge by introducing a novel material system: a 3D MXene network on a porous ceramic backbone. The backbone dictates the network's 3D architecture while providing mechanical strength, gas/liquid permeability, and other beneficial properties. Freeze casting is used to fabricate a silica backbone with open pores and controlled porosity, a MXene dispersion is infiltrated into the backbone using capillary flow, and the system is dried to conformally coat the pore walls, creating an interconnected 3D‐MXene network. The fabrication approach is reproducible, and the MXene‐infiltrated porous silica (MX‐PS) system is highly conductive (e.g., 340 S·m−1). The electrical conductivity is controlled by the porosity distribution, MXene concentration, and infiltration cycles. Sandwich‐type supercapacitors with MX‐PS electrodes produce excellent areal capacitance (7.24 F·cm−2) and energy density (0.32 mWh·cm−2) with only 6% added MXene mass. This approach of creating 3D architectures of 2D nanomaterials will significantly impact many engineering applications.This article is protected by copyright. All rights reserved