Bioelectricity provides electrostimulation to regulate cell/tissue behaviors and functions. In the human body, bioelectricity can be generated in electromechanically responsive tissues and organs, as well as biomolecular building blocks that exhibit piezoelectricity, with a phenomenon known as the piezoelectric effect. Inspired by natural bio‐piezoelectric phenomenon, efforts have been devoted to exploiting high‐performance synthetic piezoelectric biomaterials, including molecular materials, polymeric materials, ceramic materials, and composite materials. Notably, piezoelectric biomaterials polarize under mechanical strain and generate electrical potentials, which can be used to fabricate electronic devices. Herein, we propose a review article to summarize the design and research progress of piezoelectric biomaterials and devices toward bionanotechnology. We first introduce the functions of bioelectricity in regulating human electrophysiological activity from cellular to tissue level. Next, recent advances as well as structure‐property relationship of various natural and synthetic piezoelectric biomaterials are provided in detail. In the following part, we systematically classify and discuss the applications of piezoelectric biomaterials in tissue engineering, drug delivery, biosensing, energy harvesting, and catalysis. Finally, the challenges and future prospects of piezoelectric biomaterials are presented. We believe that this review will provide inspiration for the design and development of innovative piezoelectric biomaterials in the fields of biomedicine and nanotechnology.This article is protected by copyright. All rights reserved