Multifunctional materials have received increasing attention in recent years. Owing to their inherent biological nature and piezoelectric properties, piezoelectric biomaterials are considered as promising candidates for applications in biomedical systems. The rational material design is important to enhance their piezoelectric and biological activity. The recent development of piezoelectric viruses, peptides, and other polymeric biomaterials is reviewed. Fabrication methods, morphological features, and piezoelectric properties of these biomaterials are presented. The effects of growth direction, phase, and polarization of piezoelectric biomaterials on their piezoelectric activity are discussed. The applications of piezoelectric biomaterials in the fields of nanogenerators, energy-storage devices, sensors, and tissue engineering are provided. The challenges and perspective of piezoelectric biomaterials are provided at the end.