Inspired by the principles of bioelectricity and signal transmission in neurons, a multilayer laminate consisting of flexible solid polymer electrolyte membranes (PEM) and carbonaceous electrodes were developed. The present flexoelectric PEM elastomer is capable of generating electricity via ion polarization/depolarization involving ion displacement during PEM bending, i.e., mechano-electrical energy conversion, and therefore may be applicable for harvesting energy from natural resources such as wind, tidal waves, and/or rolling tires and sensors. Flexoelectricity operates based on the principle of ‘bending’ piezoelectricity, wherein electricity is produced via ion polarization during mechanical deformation. The ‘converse’ effect of electro-mechanical energy conversion is also observed, which may find applications in soft robotic actuators. To determine the flexoelectric property of the flexoelectric assembly, a unique experimental setup has been designed by combining dynamic mechanical analyzer (DMA) and Potentiostat. A very high flexoelectric coefficient (~323 µC/m) was observed for the present solid PEM elastomer, i.e., a measure of the converted mechano-electrical energy, which is the highest among all flexoelectric materials, hitherto reported. In addition, ion polarization density and electrical energy output have been evaluated for various PEM concentrations under various dynamic flexing modes, involving intermittent square wave and oscillatory sine wave as a function of frequency to establish the flexoelectric principles of viscoelastic PEM networks. Of particular importance is that the present solid PEM itself is a key component of a solid-state lithium battery capable of storing electrical energy. Furthermore, the possibility of applying the flexoelectric PEM to tires and wearable therapeutic devices will be demonstrated.