Macroporous materials with a sophisticated architecture are obtained by electrochemical deposition of gold or polypyrrole in colloidal-crystal templates. The LangmuirBlodgett technique enables assembly of sub-micrometric silica-particle monolayers on conductive gold substrates, thus leading to colloidal superstructures with an unprecedented control of their features at the single-bead-layer level. This allows the integration of deliberate planar defects or the elaboration of well-defined gradients in terms of sphere size. Controlled infiltration using electrochemical deposition preserves the architecture of the original templates and leads to inverse opals with well-defined pore structures after the removal of the inorganic particles.