In the last decade, the polymeric poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) semiconductor has been widely studied for their electrical and electrochemical properties and used in various applications such as flexible and transparent electrodes, optoelectronics and thermoelectric devices. Here, we report the intrinsic electromechanical coupling in trilayered stainless steel/PEDOT:PSS/Aluminum composites. The PEDOT:PSS thin film integrated in the multi‐layer serves as the transduction material itself and yields a remarkable flexoelectric‐like response when the cantilever shaped‐ device assembly is subjected to beam bending. Two orders of magnitude larger flexoelectric coefficients (up to μ′12 = 6 μC/m) were obtained for semiconducting PEDOT:PSS thin films, in comparison with those measured for insulating polymers. Besides, it is observed that flexoelectric effect may be enhanced when the conductivity of the trilayer device increases to a certain extent, especially after a simple dilution treatment that induces partial removal of excess hydrophilic PSS. These first results may open a new avenue for simply preparing flexible and highly sensitive curvature sensors with single electroactive semiconducting polymer layer between metal electrodes.