In ferroelastic materials, the existence of degenerate strain states leads to the formation of nanoscale microstructures, such as domain boundaries (twin walls) and tweed. As the symmetry properties of microstructures differ from those of the bulk, they may dramatically change the macroscopic properties of a crystal. In addition, they are likely to have functional properties (ferroelecricity, piezoelectricity, magnetism, conductivity and rapid chemical transport) that are absent in the bulk. The existence of functional properties of twin walls, along with the advances in nano-scale characterization, has opened the door to domain boundary engineering, which aims to use domain boundaries as active elements in device materials. Hence, this relatively new field puts ferroelastic twin walls and possibly tweed at the heart of future electronic devices. Ferroelasticity is very common among minerals. Similar to man-made materials, the same crystallographic principles apply, which means that there are many minerals that await discovery for their functional properties. Thus, this review aims to raise attention to the discovery of minerals with functional microstructures. The current development of functional twin boundaries and tweed structures in physics and materials sciences is compared with the traditional observation of such structures in minerals. With an emphasis on chemical transport and piezoelectric/ferroelectric behaviour, examples of functional microstructures are given from both man-made materials and minerals in addition to a discussion of the origin of polar twin walls and the introduction of a recent experimental technique, resonant piezoelectric spectroscopy (RPS), for their discovery.