Poly(vinyl alcohol)(PVA)/pullulan/titanium dioxide($TiO_2$) composite nanofibers were produced at different $TiO_2$ concentrations(1 and 3 wt.%) using the electrospinning method. The parameters of electrospinning including polymer contents, voltage and tip-to-collector distance(TCD) were optimized for fabrication process. The study showed that the best condition to make PVA/pullulan nanofiber and effect of $TiO_2$ nanoparticles. The PVA/pullulan/$TiO_2$ nanofibers were characterized by scanning electron microscope(SEM), transmission electron microscope(TEM), Thermogravimetric analysis (TGA) and X-ray diffraction(XRD).