Based on the effect of molecular orientation on the barrier property, a novel method of producing high barrier Polyvinyl Chloride (PVC) packaging material was proposed in this paper. Samples of different orientation degrees were prepared by a self-developed lamination extrusion machine and the properties of those samples were investigated deeply. The micro morphologies showed that the samples were of high compatibility between layers. The tensile tests indicated that the tensile strength along the extrusion direction was improved greatly by the effect of lamination components, and with the increase of the number of lamination components, the effect was more obvious. The tensile strength of 9-layers and 81-layers PVC sheets had increased by 6.19% and 10.84% respectively than traditional extrusion sheets (1-layer). The gas-permeability tests showed that, compared with the traditional sheets, the water vapor barrier properties of 9-layers and 81-layers samples had increased by 5.79% and 36.98%, and the oxygen barrier properties were enhanced by 32.46% and 55.81% respectively. Finally, the samples were tested by X-ray Diffraction (XRD) technique. The findings confirmed that the effect of flow shear in the channels of the lamination extrusion device made the PVC polymer chains highly oriented, thus improving their comprehensive performance.