Nanoporous alumina spheres with an ordered hole arrangement were prepared through a two-step anodization of small Al particles. The hole periodicity in the ordered anodic porous alumina could be controlled by adjusting the anodizing conditions. Nanoporous hollow spheres were also obtained by removal of residual Al in an etchant. Additionally, nanoporous spheres loaded with Au nanoparticles on their surfaces were obtained through electrochemical or chemical deposition of Au nanoparticles. The obtained Au/alumina composite hollow spheres were used as a substrate for surface-enhanced Raman scattering measurements.