The invention provides a preparation method of an organic electroluminescence device. The method is characterized by comprising the following operation steps: cleaning a conductive anode substrate, and carrying out spin coating on the conductive anode substrate to prepare a hole injection layer. The specific preparation method comprises the following steps: adding a rhenium oxide, azo materials, a zinc oxide and polytetrafluoroethylene to a solvent, mixing the rhenium oxide, the azo materials, the zinc oxide and the polytetrafluoroethylene evenly to obtain a mixture; carrying out spin coating of the mixture on the conductive anode substrate and drying the mixture at 50-200 DEG C for 10-30 minutes to obtain a hole injection layer, wherein the hole injection layer has a nano network structure and the aperture of the nano network structure is 100-150nm; and sequentially preparing a hole transport layer, a luminous layer, an electron transport layer, an electron injection layer and a cathode on the hole injection layer through evaporation, thereby obtaining the organic electroluminescence device.