Local structural disorder in crystalline materials plays a crucial role in understanding their properties. The means to study structural disorder is diffuse scattering (DS). Even though DS was observed since the early days of X-ray diffraction the weak intensity and the sheer number of different kinds of disorder hindered the development of a unique solution strategy. However, the advent of X-ray and neutron synchrotron sources together with recent advances in automated electron diffraction techniques have unraveled a new world in between Bragg peaks where a wealth of information is available.

In this thesis electron diffraction is used to explore the different kinds of DS in three-dimensions, for several perovskite ferroelectric ceramics. Based on the information presented in the reconstructed 3D reciprocal space volumes, disordered atomic structures were proposed and verified by the calculated electron diffraction patterns. A complex structural model for the local disorder in 85Na_0.5Bi_0.5TiO₃-10K_0.5Bi_0.5TiO₃-5BaTiO₃ piezoceramic was developed by analyzing the morphology and intensity of electron DS in 3D. Next, the influence of potassium-content on the octahedral-tilt disorder for three different piezoceramics was studied by a combination of dark-field imaging and electron diffraction. Further on, the temperature-dependence of electron DS for 95Na_0.5Bi_0.5TiO₃-5BaTiO₃ piezoceramic revealed a local structural phase transition that was correlated with the depolarization mechanism. Lastly, strong electron DS was recorded from a Pb-based relaxor and simulations of disordered atomic structures showed that the local structure resembles a dipolar glass state. These demonstrate that electron diffraction is a powerful tool for the study of local structural disorder in crystalline materials, especially for ceramics. The major advantage is that we are able to record single-crystal electron diffraction data from individual grains. Moreover, since we are analyzing a 3D reciprocal volume several orientations can be studied simultaneously and we are not limited to zero-Laue zones. Finally, the models for local structural disorder provided valuable insight into how macroscopic properties are influenced by local structural disorder, in addition to the average structure.