The translation of the well-known reversible electrochemical switching of viologen species from solution to the solid state may open enormous possibilities for developing electrically responsive materials. In this work, we present and discuss the electrochemical response of a viologen derivative, 1,1′-dipropyl-4,4′-bipyridinium bis-hexafluorophosphate (Bpy2+), embedded into a polyurethane fibrous matrix. The results showcase the possibility of stimulating electrochemically the active molecule inside the polymer fibers, both in random and aligned configurations, retaining the fibrous morphology and structure while avoiding the use of conductive polymers and ionic liquids, thus opening a new scenario in electrochemically responsive soft actuators.