A facile three-step method is developed to prepare new titania fibers with various special structures using a standard electrospinning equipment. After the traditional electrospinning, a treatment process, such as storing in air and soaking in water, for electrospun composite fibers is added before the calcination. Based on a given electrospinning solution and corresponding composite fiber, the structure of titania fiber is easily adjusted to be rough surface, fiber-in-tube, or a string of many particles by controlling the treating parameters and the calcination temperature, so this method shows a great potential of producing ceramic nanofibers with controlled structures for a large-scale production using a standard electrospinning equipment. The origin behind the morphological change of titania electrospun fibers is intensely studied. The results indicate that the surface structure of titania electrospun fiber formed during the storing period, will become the key factor on the formation of special titania fiber structure during the calcination process with different temperatures.