This article provides a comprehensive overview of piezo‐ and ferro‐electric materials based on organic molecules and organic–inorganic hybrids for mechanical energy harvesting. Molecular (organic and organic–inorganic hybrid) piezo‐ and ferroelectric materials exhibit significant advantages over traditional materials due to their simple solution‐phase synthesis, light‐weight nature, thermal stability, mechanical flexibility, high Curie temperature, and attractive piezo‐ and ferroelectric properties. However, the design and understanding of piezo‐ and ferroelectricity in organic and organic–inorganic hybrid materials for piezoelectric energy harvesting applications is less well developed. This review describes the fundamental characterization of piezo‐ and ferroelectricity for a range of recently reported organic and organic–inorganic hybrid materials. The limits of traditional piezoelectric harvesting materials are outlined, followed by an overview of the piezo‐ and ferroelectric properties of organic and organic–inorganic hybrid materials, and their composites, for mechanical energy harvesting. An extensive description of peptide‐based and other biomolecular piezo‐ and ferroelectric materials as a biofriendly alternative to current materials is also provided. Finally, current limitations and future perspectives in this emerging area of research are highlighted. This perspective aims to guide chemists, materials scientists, and engineers in the design of practically useful organic and organic–inorganic hybrid piezo‐ and ferroelectric materials and composites for mechanical energy harvesting. Mechanical Energy Harvesters: The review overviews the recent developments in piezoelectric and ferroelectric organic molecules and organic–inorganic hybrid materials for energy harvesting applications. The advantage of them lies in their solution‐phase synthesis, light‐weight nature, thermal stability, mechanical flexibility, and high polarization that enables them to serve as efficient generators. These aspects are discussed in detail, and future directions indicated.