The electro-optical features of the PDLC films applied with a low-frequency square wave voltage were investigated. The transmittance curves indicated the double frequency of the applied voltage at 0–50 Hz, which resulted from the relaxation of an internal electric field polarized by ions in LC droplets. When the local electric field was reversed, the internal polarization electric field could be maintained and superimposed on the local electric field. The relaxation of the internal polarized electric field resulted in the relaxation of the transmittance. Furthermore, the transmittance curves changed with the frequency of the applied voltage.