Perovskites and related compounds constitute the majority of commercial piezoelectric ceramics. Typically, most publications note the structure, grain size and properties of piezoelectrics but often very little is reported about their domain and domain wall structure. In many commercial systems, it is the motion or vibration of the domain wall which dominate the piezoelectric and electromechanical coupling coefficients, the so-called extrinsic contribution. This article discusses mechanisms relating to structure and domain wall structure which either suppress or enhance extrinsic contributions. Consideration is given to the multiferroic nature of some systems in which octahedral tilt in addition to ferroelectric phase transitions occur. The domain structure at and adjacent to the morphotropic phase boundary in several well known systems is also discussed.

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