Self‐assembled polyaniline nano‐microspheres with a low cytotoxicity were synthesized by a simple temperature controlling method and uniformly distributed on animal hairs that had been chemically functionalized with 4‐aminothiophenol. The resulting hybrid hairs were found to exhibit unique characteristics that help reduce the adhesion of natural pollen grains and spores. This new type of natural hybrid material shows great promise for the development of anti‐pollen fiber products capable of protecting against many different types of environmental pollutant.