The paper describes a new approach to producing hybrid composite materials with multiscale morphologies. We doped polymer submicrometer spheres with semiconductor or metal (CdS or Ag, respectively) nanoparticles and used these doped microspheres as the functional building blocks in production of hybrid periodically structured materials. The preparation of hybrid polymer particles included the following stages: (i) synthesis of monodisperse polymer microspheres, (ii) in situ synthesis of the inorganic nanoparticles either on the surface, or in the bulk of the polymer beads, and (iii) encapsulation of hybrid microspheres with a hydrophobic shell. We demonstrated that by changing the composition of the polymer beads good control could be achieved over the size of the nanoparticles.