The invention relates to a preparation method of a flexible OLED light-emitting device based on the anode structure of a novel laminated film. The OLED light-emitting device comprises a light-emitting layer and a cathode positioned on one side of the light-emitting layer. The method comprises the following steps: S1, growing graphene on a copper foil by adopting a chemical vapor deposition method; S2, transferring the graphene onto a flexible PET substrate; S3, putting the prepared graphene/PET into an HNO3 solution for soaking, and then drying; S4, spraying a PEDOT:PSS solution on the treated graphene, then putting on a heating plate for drying; and S5, putting a prepared graphene/PEDOT:PSS composite film into a vacuum cavity, adopting a vacuum evaporation technology to heat and plate the graphene/PEDOT:PSS composite film on the side, at the back of the cathode, of the light-emitting layer as an anode, and thus preparing the OLED light-emitting device. The graphene serves as the anode of a photoelectric device, so that the anode has the characteristics of high carrier mobility, good mechanical flexibility, high transmittance and the like; and the PEDOT:PSS enables the anode to be of the characteristics of high conductivity, high work function and high transmittance.