In order to investigate the molecular vibrations and structure variations of PVC gels with applied electric fields, a mechanical measurement (combined tensile and shear test) was proposed, and the Fourier transform infrared (FT-IR) spectrometry and in situ Raman spectroscopy were conducted to clarify the mechanism of electric-field-induced local layer structure in PVC gel and its relationship to gel creeping deformation. As a result, the electric-field-induced local layer structure and the migration of the solvent-rich phase in PVC gels were clarified. The layer of PVC gel clinging to the anode is softer than that near the cathode. The peaks of FT-IR spectra were shifted and changed in the gel surface on the anode and cathode. Using the in situ Raman spectroscopy, it is found that the intensity of the whole Raman spectra was reduced from the cathode to the anode, and the elastic modulus of the gel on the anode was smaller than that on the cathode. All of the results indicated that the electric field induced the local layer structure and caused the asymmetric actuation behavior in PVC gel actuators.