Hollow titania containing multilayer nanofibers was fabricated through the combination of electrospinning with layer-by-layer technique. Two different solvents, methylbenzene and THF were used to remove the template. The morphology of the obtained hollow multilayer nanofibers confirmed that THF is better than methylbenzene. The obtained hollow multilayer fiber has a diameter of about 700 nm and its shell thickness is about 140 nm. FTIR spectra show the fabrication of multilayer nanofibers. XPS measurement indicates that TiO2 nanoparticles can be assembled successfully. The obtained multilayer hollow nanofibers have highest photocatalytic activity to degrade methylene blue solution comparing with the TiO2 film due to their unique hollow structure. (C) 2008 Elsevier Ltd. All rights reserved.