AbstractIcing accretion on the surface of an aircraft not only increases the weight but also causes changes in the surface shape, so there is an urgent need for anti‐icing/deicing without shutdown. Here, a graphene‐based film with light weight, super‐hydrophobicity, high electric heat, and durability, which has both anti‐icing properties and electrothermal deicing capability, is proposed. The film is prepared with 1H,1H,2H,2H‐perfluorodecyltrichlorosilane (FDTS)‐modified SiO2/rGO wrinkles, and it has a micro‐nanoscale hierarchical structure. Moreover, the superhydrophobic properties of the film can be controlled by adjusting the wrinkle size. Because of its good water repellency, the film can prevent and delay the freezing of water droplets at low temperatures. At −10 °C, compared to a smooth rGO film, the icing time of 10 µL supercooled water droplet on the micro‐nanoscale hierarchical structured film can be delayed by ≈8.3 times, and the ice adhension decreases greatly. In addition, the film exhibits high‐efficiency electrothermal properties. At −10 °C, under a low voltage of 15 V, the film can be heated rapidly to achieve rapid deicing and defrosting. The graphene‐based micro‐nanoscale hierarchical structure shows great potential in the field of sky anti‐icing and real‐time deicing.