Chemical vapor deposition of carbon nanotubes by catalytic decomposition of acetylene on V2O5 microtube crystals is presented. The catalyst was prepared by laser irradiation of vanadium sheets and treated with cobalt acetate solution. The carbon deposits generated on this novel type of catalyst were characterized by transmission electron microscopy measurements. Both carbon nanofibers and carbon nanotubes were found to be formed. This catalyst system, generated by the combined laser irradiation and chemical impregnation methods, is a new and promising way to study the differences in the mechanism of the generation of nanostructures.