The accumulation of ice can cause damage to various equipment, resulting in numerous economic losses. One promising solution for anti/de‐icing is the use of superhydrophobic materials powered by solar energy. In this study, a multilayer superhydrophobic photothermal materials with anti/de‐icing ability is prepared. First, an epoxy resin (EP) substrate with microstructure is prepared by the template method. Then carbon black (CB) nanoparticles are sprayed on the substrate as the photothermal layer. Finally, fluorine‐modified resin is dip‐coated as the hydrophobic modified layer. The light absorption of this material is 1.6 in the wavelength range of 400–2000 nm. The surface temperature rose to 114.2 °C within 270 s under 1 sun illumination. Additionally, the materials can respond to light stimulation and exhibit shape memory, with a shape recovery rate close to 100%. The air cushions in the micro‐nanostructures delayed the droplet freezing time by nearly two times. The good photothermal properties endowed the materials with photothermal de‐icing performance, which improved the de‐icing efficiency by almost 2.2 times. Furthermore, the materials demonstrate outstanding durability that can resist to mechanical wear, acid‐base corrosion, and UV aging, thermal stability, and self‐cleaning properties, making it highly suitable for outdoor equipment applications.