In this work, the N-doped TiO2/C composite is successfully prepared using electrospinning technique. TEM, XPS and Raman techniques are used to characterize the morphologies and microstructure of the as-fabricated composite, confirming that the incorporation of N into TiO2/C can not only reduce the d-spacing of TiO2 nanocrystals, but also can transform it into another TiO2 crystal form. Furthermore, amorphous carbon in this composite can be transferred to graphite under the effect of TiO2 during calcination processes. The N-doped TiO2/C sample with variable pore sizes exhibit the largest specific surface area, and the crystal forms of TiO2 are close related to the value of specific surface area and the pore sizes.