Piezoelectricity is associated with crystalline materials that have noncentrosymmetric crystal units. This work reports the electroactive properties of poly(epsilon-caprolactone) (PCL) membranes produced by electrospinning. The individual PCL fiber shows an apparent piezoelectric constant of 5 +/- 2 pm.V-1 with a longitudinal piezoelectric voltage coefficient of 0.25 Vm.N1-. Further, the PCL flexible electronic skin device exhibited superior mechano-sensitivity of 0.098 V.kPa(-1), had the ability to measure small forces (1 mN), presents a remarkable output voltage stability (>16 000 cycles), and could accurately monitor human gait. The overall electroactive properties create opportunities in the development of environmentally friendly and low-cost energy nanoharvesting and wearable devices for human gait applications.