Materials with complex 3D morphologies have broad applications in photonic crystals, filtration, sensing, biomedicine, metamaterials, and catalysis as well as energy conversion and storage. Such applications are enabled by the materials’ high surface-to-volume ratio, improved connectivity, functional pore interface, adjustable pore accessibility, and mechanical stability. Sophisticated 3D mesostructures with critical lattice orientations, transport pathways, and chemical compositions in bulk materials provide an effective platform for revealing the relationship between structure and properties. The unique properties of soft materials—large response to small perturbations, self-assembled ordered structure, low energy consumption for altering structure—make them widely used to create controllable 3D structures. However, due to the inherently weak mechanical property, soft materials usually can’t withstand harsh engineering conditions, such as high temperature, stress or chemical environments. Here, we rely on blue phase liquid crystals, which combine the order of solid molecular crystals and the fluidity of liquids, giving them highly ordered 3D cubic symmetries and rapid assembly kinetics.