As climatic conditions worsen and time passes, icing becomes an unavoidable issue. Drawing inspiration from the thermal regulatory properties inherent in polar bear fur, we introduce a biomimetic three-layer film. This film comprises a hydrophobic shield, a photothermal conversion layer, and an insulating layer through electrospinning. The multilayered micro/nanostructure within this film amplifies its light absorption capabilities, achieving an average absorption rate of 96.27 % across wavelengths ranging from 200 to 2500 nm. Thanks to the insulation layer's thoughtful design, the film boasts high photothermal conversion efficiency. When exposed to solar radiation for 360 s at an ambient temperature of 20 °C, its surface temperature swiftly climbs to 98.3 ± 1.1 °C. The film's anti-icing capabilities are evidenced by the fact that a droplet of water takes 2964.7 s to freeze on its surface, which is approximately 118 times that of aluminum. Additionally, it demonstrates excellent photothermal de-icing performance, swiftly eliminating thick layers of ice or frost under sunlight. Moreover, this film maintains its anti-icing and hydrophobic qualities even after multiple icing and de-icing cycles, as well as durability testing. It also possesses self-cleaning properties. Given its outstanding performance, this film has tremendous potential for long-term outdoor anti-icing applications.