AbstractElectromechanical effects are ubiquitous in biological and materials systems. Understanding the fundamentals of these coupling phenomena is critical to devising next‐generation electromechanical transducers. Piezoelectricity has been studied in detail, in both the bulk and at mesoscopic scales. Recently, an increasing amount of attention has been paid to flexoelectricity: electrical polarization induced by a strain gradient. While piezoelectricity requires crystalline structures with no inversion symmetry, flexoelectricity does not carry this requirement, since the effect is caused by inhomogeneous strains. Flexoelectricity explains many interesting electromechanical behaviors in hard crystalline materials and underpins core mechanoelectric transduction phenomena in soft biomaterials. Most excitingly, flexoelectricity is a size‐dependent effect which becomes more significant in nanoscale systems. With increasing interest in nanoscale and nano‐bio hybrid materials, flexoelectricity will continue to gain prominence. This Review summarizes work in this area. First, methods to amplify or manipulate the flexoelectric effect to enhance material properties will be investigated, particularly at nanometer scales. Next, the nature and history of these effects in soft biomaterials will be explored. Finally, some theoretical interpretations for the effect will be presented. Overall, flexoelectricity represents an exciting phenomenon which is expected to become more considerable as materials continue to shrink.