Polyviologens (PVs) are used as potential templating agents. They were prepared and then incorporated into a silica matrix via base-catalyzed hydrolytic sol-gel reaction. The resultant polymer hybrid material is amorphous aggregates of roughly spherical silica nanoparticles. In this article, we describe an experimental system designed to examine an assembly of nanoparticles in a wide range of process engineering applications. These applications include harvesting from solutions of nanoparticles into green parts and subsequent sintering into finished components. The system is based on an X-ray microtomography with a spatial resolution down to 5 mm. The application of the microtomography technique to the study of thermally induced morphological changes in silica-polymer hybrid nanoparticles is described under different experimental conditions.