The invention discloses an anti-icing composite coating and a manufacturing method thereof. The anti-icing composite coating comprises three layers, wherein an inner layer is an organic silicon modified epoxy resin layer, a middle layer is a polyelectrolyte salt layer and an outer layer is a fluorine-silicon modified acrylic ester layer. The anti-icing composite coating is coated on the surfaces of components, such as high-voltage cables, iron towers, communication lines, aircrafts and the like, the adhesive force between the inner layer and a substrate can be increased due to the inner layer, icing can be slowed down due to ions ionized by the middle layer, and the adhesive force of ice on the surface and the icing quantity of the surface can be reduced due to the super hydrophobicity of the outer layer. The anti-icing composite coating has excellent bonding force on the substrate and higher heat conductivity, the surface of the outer layer has low surface tension, high hydrophobicity and high icing resistance, and the adhesive force of water and ice can be reduced to the maximum, thus the water and the ice can be easily removed; meanwhile, the middle layer can ionize ions to delay the adhesion of the ice under severe environment, thus the purposes of icing prevention and ice removal are realized. The manufacturing method disclosed by the invention has the advantages of easiness, feasibility, convenience for control, lower cost, and excellent use effect during engineering.