In the present paper regular systems of silicon and platinum assemblies have been fabricated in a three-dimensional (3D) void sublattice of synthetic opal. The detailed TEM and HREM structure study of ‘opal-Si’ and ‘opal-Pt-Si’ composites was carried out. It was found that in regular composites ‘opal-Si’ the silica spheres were covered uniformly with a nanocrystalline silicon layer of up to 25-30 nm in thickness. To form the Pt-Si contact the silica spheres were coated with platinum layer before embedding silicon. The results obtained demonstrate a possibility of creating 3D multilayer semiconductor structure (p-n junctions, Schottky barriers etc.) on the inner surface of opal voids.