Kesterite quaternary semiconductor Cu2ZnSnSe4 nanocrystals were successfully prepared via a relatively simple electrospinning route and characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). Semiconductor Cu2ZnSnSe4 nanofibers were obtained for PVB/ Cu2ZnSnSe4 precursor at an applied voltage of 20 kV after annealing treatment at 500 degrees C for 2 h. The optical property of Cu2ZnSnSe4 nano crystals was also recorded by means of UV-vis absorption spectroscopy. It was shown that the dimension effect of composites could be enhanced by increasing the electrospinning conditions (voltage, distances, concentrations, viscosity) and the CZTSe nanofibers prepared at annealing process exhibited more intense optical properties. Temperature dependent studies were conducted and the annealing of composites was found to be the key factor in determining the phase formation. (C) 2016 Elsevier B.V. All rights reserved.