A novel method has been developed to synthesize gold nanoparticles with tunable size and morphology supported on both inner and outer surfaces of poly(o-phenylenediamine) (PoPD) hollow microspheres, which act as both reductant and template/stabilizer. The size of gold nanoparticles supported on shells of PoPD hollow microspheres can be tuned from 3 to 15 nm by changing the concentration of the gold source, HAuCl4. Gold nanorods supported on shells of PoPD hollow microspheres can also be fabricated by introducing a well-known seed-growth strategy. In addition, silver nanoparticles supported on shells of PoPD hollow microspheres can also be successfully fabricated using the same strategy, which indicates the diversity of this proposed method for polymer hollow microspheres supporting noble metal nanoparticles. The products are characterized by X-ray diffraction and contact angle analysis. Furthermore, the catalytic activity of the obtained PoPD-microsphere-supported gold nanoparticles for aerobic alcohol oxidation is investigated. The results demonstrate that such polymer-supported gold nanoparticles can be used as reusable catalysts with high catalytic activity for aerobic alcohol oxidation in water.