Passive cooling materials, as a promising choice for mitigating the global energy crisis, have limited use as their cooling effects are usually weakened or lost by dust contamination. In this study, a passive cooling polyethylene (PE) film with self-cleaning properties is prepared by picosecond laser ablation. Numerous root-like hierarchical porous micro/nano-structures were obtained on the double side of the PE film. The outside (toward air) shows excellent self-cleaning, corrosion resistance, and anti-friction properties. The inside (towards crops) further reduced the transmittance and water vapor evaporation (keeping the soil moist). Compared with the pristine PE film, the transmittance of the as-prepared double-sided micro/nano-structured PE film decreased by about 40%. In addition, during the crop cultivation experiment, the temperature of the crop leaves was reduced by 2.7–7 °C and showed a higher plant height and greater leaf width under the cover of the laser-treated film. This demonstrates that the passive cooling PE film has an excellent temperature regulation ability and good practical application effects. This study proposes a simple strategy based on a picosecond laser for the preparation of passive cooling materials, which are beneficial for alleviating energy crises and promoting sustainable development.