The ability to provide the energy needed while keeping the product ergonomic, lightweight and nonâintrusive, is the ultimate challenge for wearable technologies. In this work, silk fibroin (SF) is electrospun and immersed in liquid methanol (MeOH) over 3 and 48 h. A phase transformation from waterâsoluble αâhelix (silk I) to insoluble ÎČâsheets (silk II) is observed, increasing the protein crystallinity and the membrane stability against aqueous environments. The phase transformation from silk I to silk II leads to a reorganization of the polymer chains inside the protein fibers, which influences the dipolar reorientation of the SF molecules. A costâeffective energy harvester device is built, showing an openâcircuit output voltage of 4.5 V, a power density around 1 ”mW cmâ2, with an efficiency up to 6%, and a mechanoâsensitivity of 0.078 ± 0.01 V kPaâ1. This work provides new insights into the effect of the stabilization process of the SF membranes and its influence on the electroactive properties of the protein. Overall, the electromechanical and energy harvesting performance of the SF membranes opens new opportunities for applications as wearable selfâpowered microelectronics, with the potential to be fully integrated inside clothing, with potential applications in personalized healthcare devices and sports training systems.