An internally ultrastructured Al- and Zr-oxide hybrid was developed into a nanofiber. As a precursor for the generation of nanofiber, a hybridized sol was prepared using the Pechini-type sol-gel process, whereby the Al- and Zr-metallic ions were to be efficiently distributed and stabilized within the polymeric network. The hybridized sol was subsequently electrospun and heat treated to a nanofiber with diameters of tens to hundreds of nanometers. The internal structure of the nanofiber was organized at the molecular level, with the Al- and Zr-oxide regions being interspaced at distances of less than ten nanometers. This ultrastructured Al- and Zr-oxide hybrid nanofiber is considered to be potentially applicable in numerous fields.