Abstract: Polyvinyl alcohol has been widely used as a packaging substrate, but its water resistance is poor. Improving the water resistance of polyvinyl alcohol is critical. In this study the major modification methods were to add nano-materials, fats or oil substances and crosslinking agents. Functional nanomaterials have small size, large surface area that combine the hydroxyl group with polyvinyl alcohol to reduce the hydrophilic. Beeswax is a composition material by fats and oils. It has higher melting point, acid corrosion, water-blocking performance characteristics. Furthermore it can form a stable emulsion, resulting in long shelf life, high solid content, good dispersion and other fine features. Beeswax is widely used in fruit and vegetable preservation, fruits and vegetables can reduce the water loss rate and respiration. In this experiment a stable emulsion with polyvinyl alcohol (PVA) was formed from hydrophobic of beeswax and the small surface area, high activity of nanosized α-Fe2O3 to reduce film water vapor transmission rate of packing material of polyvinyl alcohol efficiently. By adding beeswax and nanosized α-Fe2O3 to polyvinyl alcohol based composite coating material, the impacts of film-forming water vapor transmission rate and its interaction was studied through analyzing the response surface between the two experimental factors. The result showed that the increasing amount of beeswax and then nosized α-Fe2O3 could reduce the water vapor transmission rate of polyvinyl alcohol composite material effectively. Therefore two materials have mutual impacts (P<0.05). The beeswax dosage was 0.739 g/100mL, and nanosized α-Fe2O3 was 0.04 g/100mL based on the regression optimization. The water vapor transmission rate reached the lowest point, which was lower than the former Liquid paraffin-polyvinyl alcohol film 73.76% (P<0.05). Meanwhile, nanosized α-Fe2O3 could be used as a new nano-material. Its narrow band gap generally was 2.2 eV, the maximum absorption wavelength was 560 nm that increases photocatalytic reaction in the utilization of light. The nanosized α-Fe2O3 was able to produce ?OH under the visible reaction which has strong oxidation ability to react with most organic degradation and bacterial until it was converted to CO2 and H2O. The optimized films have obvious antibiotic effect. In photocatalytic conditions, the total number of E. coli colonies can drop an order of magnitude. This study could be beneficial for developing better quality of preservation, and packaging film materials.