Hollow metal oxide fibers [TiO2 and Fe2O3] have been prepared by using activated carbon fibers [ACFs] as the templates, through a simple impregnation and heat treatment. The resulting products, as compared to ACFs, possessed not only a similar morphological feature upward to the micrometer scale but also different surface nanostructures with unique morphology. The TiO2 fibers displayed overlapped “wormlike” surface and a hierarchical structure with two distinguishable layers, the inner layer and the outer layer, which were composed of the particles of 7 and 15 nm, respectively. It was also found that the reaction temperature had a significant effect on the TiO2 surface morphology. The Fe2O3 fibers exhibited a rough and crinkle-like surface and were also composed of hierarchical particles. Both TiO2 and Fe2O3 fibers possessed the hierarchical pore structure with mesopores in the walls of the large hollow channel. Such porous architecture favored the resultant TiO2 with better apparent photoactivity than P25 titania for degradation of gaseous acetone and would also make the materials useful for further application in other fields.