A practical and multipurpose technique has been developed to create 3D free-standing nanocomposites with well controlled nano- and micro-scale features. The internal organization, controlled molecular structure and versatility of conventional layer-by-layer (LBL) assembly techniques have been combined with the nearly perfect order and control over interconnecting channels of inverted colloidal crystals to create a hierarchically controlled 3D nano-assembly. LBL assembly of polyelectrolytes and nanoparticles is performed on polystyrene beads arranged in a hexagonal crystal lattice. Upon dissolution of the colloidal crystal a structure with multi-scale and multidimensional response to external stimuli is produced. This simple, low cost, highly repeatable fabrication technique allows for optimized surface area, mass transport, and mechanical properties. The resulting composite displays many properties of natural materials which often exhibit hierarchical combination of nano- and microscale structural elements. Additionally, fairly large 3D samples of hierarchical nanocomposites can be produced and tested in this way. As 2D LBL assembled films have been employed over many disciplines, the self-supporting 3D structure produced has properties that are extremely attractive to multiple disciplines including tissue engineering, catalysis, porous, high strength materials, and aviation.