We report on structural, morphological and ordering properties of Fe2O3/TiO2 nanoparticles embedded in SiO2-based multilayers. We investigated the structure of these systems by X-ray diffraction and grazing incidence small angle X-ray scattering after post-growth annealing. We found that the presence of TiO2 promotes the growth and crystallization of the nanocrystals of Fe2O3. In multilayers containing both Fe2O3 and TiO2, crystalline nanoparticles create partially ordered three-dimensional arrays. (C) 2011 Elsevier B.V. All rights reserved.