X-ray and neutron diffraction have become powerful characterization tools in materials research. Their leading use in the characterization of piezoelectric ceramics includes the determination of structure, phase evolution, crystallographic texture, and lattice strain. The inherent electromechanical coupling of piezoelectric materials also allows the direct characterization of the converse piezoelectric effect. New advances in diffraction capabilities have recently enabled new problem solutions within this field. For example, the use of microdiffraction has the potential to characterize structural defects including cracks and domain walls. The development of time-resolved techniques has further opened doors to characterizing ferroelectrics in real-time under the application of cyclic electric fields. These recent advances as well as traditional uses of X-ray and neutron diffraction in the characterization of piezoelectric materials and the phenomenon of piezoelectricity are explored in this review. A focus is on characterization of bulk, polycrystalline ceramics, though novel approaches in thin films and single crystals are also reviewed. Challenges and future opportunities are discussed.