The invention belongs to the technical field of conductive coatings, and discloses a graphene composite conductive coating as well as a preparation method and application thereof. The coating is composed of the following materials: 5-80% of resin, 0.1-5% of graphene, 2.5-20% of copper powder, 7.2-30% of silver powder, 0.55%-3.0% of a dispersant, 17-40% of an organic solvent, 0.3-1% of an anti-settling agent, 0.3-1% of a levelling agent and 0.1-1% of a cross-linking agent; and the preparation method comprises the following steps: adding the graphene into a slowly-drying solvent, adding the dispersant, performing stirring, and performing ultrasonication; adding the ultra-fine copper powder into a slowly-drying solvent, adding the dispersant, performing stirring, and performing ultrasonication; adding the ultra-fine silver powder into a slowly-drying solvent, adding the dispersant, performing stirring, and performing ultrasonication; and adding the dispersant into acrylate polyurethane, adding the treated solutions into the acrylate polyurethane in sequence, adding the organic solvent, the anti-settling agent, the levelling agent and the cross-linking agent, performing stirring, and performing grinding. The coating provided by the invention meets the requirements of conductive performance, avoids the single use of silver, reduces costs, and has a high price/performance ratio.