This paper reviews some recent advances in small‐angle X‐ray and neutron scattering methods and their application to address complex issues in ceramic systems of technological importance. It is shown how small‐angle scattering (SAS) can be applied to ceramic systems in order to extract statistically representative microstructure information (e.g., void volume fraction size distributions, internal surface areas, pore morphologies) that complements the information obtained from diffraction methods, X‐ray microtomography, or electron microscopy. It is demonstrated how SAS studies provide insights, not obtainable by other means, on the processing–microstructure–property relationships that frequently govern technological performance.