Hierarchically porous materials are of great interest in such applications as catalysis, separations, fuel cells, and advanced batteries. One such way of producing these materials is through the process of nanocasting, in which a sacrificial template is replicated and then removed to form a monolithic replica. This replica consists of mesopores, which can be ordered or disordered, and bicontinuous macropores, which allow flow throughout the length of the monolith. Hierarchically porous metal oxide and carbon monoliths with an ordered mesopores system are synthesized for the first time via nanocasting. These replicas were used as supports for the deposition of silver particles and the catalytic efficiency was evaluated. The ordered silica template used in producing these monoliths was also used for an in-situ TEM study involving metal nanocasting, and an observation of the destruction of the silica template during nanocasting made. Two new methods of removing the silica template were developed and applied to the synthesis of copper, nickel oxide, and zinc oxide monoliths. Finally, hollow fiber membrane monoliths were examined via x-ray tomography in an attempt to establish the presence of this structure throughout the monolith.