Abstract: The hollow TiO₂/SiO₂ composite nanofibres were successfully synthesized via an electrospinning technique. The samples were studied by TGA-DTA , FTIR , XRD , SEM , TEM and EDS. The results indicate that the outer-wall of the as-prepared TiO₂/SiO₂ nanofibres is amorphous SiO₂ and the inner-wall is composed of TiO₂ nanoparticles of 50 nm in diameter . The composite hollow nanofibres are 2μm in the mean diameter and greater than 100μm in length. Their formation mechanisms were also discussed. During the calcination of composite fibres , the TiO₂ nanoparticles are diffused from the core toward the inner surface , new bonds are formed between TiO₂ nano-particles and SiO₂ shell , and composite hollow nanofibres are finally obtained.