Enhancing ion conductance and controlling transport pathway in organic electrolyte could be used to modulate ionic kinetics to handle signals. In a Pt/Poly(3-hexylthiophene-2,5-diyl)/Polyethylene?Li CF3SO3/Pt hetero-junction, the electrolyte layer handled at high temperature showed nano-fiber microstructures accompanied with greatly improved salt solubility. Ions with high mobility were confined in the nano-fibrous channels leading to the semiconducting polymer layer,which is favorable for modulating dynamic doping at the semiconducting polymer/electrolyte interface by pulse frequency.Such a device realized synaptic-like frequency selectivity, i.e., depression at low frequency stimulation but potentiation at high-frequency stimulation. Enhancing ion conductance and controlling transport pathway in organic electrolyte could be used to modulate ionic kinetics to handle signals. In a Pt / Poly (3-hexylthiophene-2,5-diyl) / Polyethylene® Li CF3SO3 / Pt hetero-junction, the electrolyte layer handled at high temperature showed nano-fibrous channels leading to the semiconducting polymer layer, which is favorable for modulating dynamic doping at the semiconducting polymer / electrolyte interface by pulse frequency. Such a device realized synaptic-like frequency selectivity, ie, depression at low frequency stimulation but potentiation at high-frequency stimulation.