Core-shell micro/nanostructured and electromagnetic functionalized polypyrrole (PPy) composites were prepared by a self-assembly process associated with the template method in the presence of p-toluenesulfonate acid (p-TSA) as the dopant, in which the spherical hydroxyl iron (Fe[OH], 0.5-5 mu m in diameter) functioned not only as the hard template, but also as the "core" of the micro/nanostructure, and the self-assembled PPy-p-TSA nanofibers (20-30 nm in diameter) acted as the "shell" (50-100 nm in thickness) of the microspheres. We found that the core-shell micro/nanostructures exhibit controllable electromagnetic properties by adjusting the mass ratio of Fe[OH] to pyrrole monomer. The micelle model was proposed to interpret the self-assembly of the core-shell micro/nanostructured composites.