Using tetrabutyltitanate as titanium source, amorphous TiO2 powder was firstly prepared by a sol–miniemulsion–gel method. Prepared powder was refluxed in basic solution and then calcined at different temperatures to synthesize titania nanofibers. The prepared samples were characterized by XRD, TG–DSC, FT–IR and TEM. The results show that when the heat–treatment temperature increases, crystallization of the titania nanofibers occurs with two Ti–OH bonds dehydrate, meanwhile morphology of the fibers is gradually obvious and ratio of length to diameter decreases. When the temperature was raised above 550 °C, titania nanofibers were sintered.