Piezoelectric materials are important for many physical and electronic devices. Although many piezoelectric ceramics exhibit good piezoelectricity, they often show poor compatibility with biological systems that limits their biomedical applications. Piezoelectric peptide and metabolite materials benefit from their intrinsic biocompatibility, degradability, and convenient biofunctionalization and are promising candidates for biological and medical applications. Herein, we provide an account of the recent progress of research works on piezoelectric peptide and metabolite materials. This review focuses on the growth mechanism of peptide and metabolite micro- and nanomaterials. The influence of self-assembly processes on their piezoelectricity is discussed. Peptide and metabolite materials demonstrate not only outstanding piezoelectric properties but also unique electronic, optical, and physical properties, enabling their applications in nanogenerators, sensors, and optical waveguiding devices.