AbstractPiezoelectric energy harvesting captures mechanical energy from a number of sources, such as vibrations, the movement of objects and bodies, impact events, and fluid flow to generate electric power. Such power can be employed to support wireless communication, electronic components, ocean monitoring, tissue engineering, and biomedical devices. A variety of self‐powered piezoelectric sensors, transducers, and actuators have been produced for these applications, however approaches to enhance the piezoelectric properties of materials to increase device performance remain a challenging frontier of materials research. In this regard, the intrinsic polarization and properties of materials can be designed or deliberately engineered to enhance the piezo‐generated power. This review provides insights into the mechanisms of piezoelectricity in advanced materials, including perovskites, active polymers, and natural biomaterials, with a focus on the chemical and physical strategies employed to enhance the piezo‐response and facilitate their integration into complex electronic systems. Applications in energy harvesting and soft robotics are overviewed by highlighting the primary performance figures of merits, the actuation mechanisms, and relevant applications. Key breakthroughs and valuable strategies to further improve both materials and device performance are discussed, together with a critical assessment of the requirements of next‐generation piezoelectric systems, and future scientific and technological solutions.