BaTiO3 xerogel hollow fibers have been prepared firstly by co-electrospinning the sol precursor, and the polycrystalline BaTiO3 ceramic hollow fibers were obtained after calcination at 1000 degrees C. The obtained hollow fibers made up of well-crystallized nanocrystals were about 400 nm to several micrometers in outer diameter. The hollow BaTiO3 fibers have been detected by means of SEM, TG, DSC, FTIR, and XRD techniques.