In this study, we synthesed two kind of TiO2 nanomaterial (nanoparticles and nanofiber) for photocatalitic degradation of methyl orange (MO) as pollutant. TiO2 nanoparticles were synthesized by sot-gel technique using titanium (IV) isopropoxide as precursor. Polyvinyl acetate (PVAc)/TiO2 hybrid nanofibers were fabricated by combining sot-gel process with electrospinning technology, which consisted of PVAc as organic segment and TiO2 as inorganic part. Crystalline phase of TiO2 nanomaterials was investigated by X-ray diffraction (XRD). The XRD results show that the TiO2 nanomaterials crystallize in anatase with some rutile phase and these consist of titanium dioxide nano-crystals. The surface structures of TiO2 nanomaterials were examined using scanning electron microscopy (SEM). SEM scanning revealed that the nanoparticle and nanofibrous structure was formed. Fourier transform infrared spectroscopy (FTIR) was employed to analyze the chemical structures of the PVAc/TiO2 hybrid nanofibers. The FTER analysis indicated the newly formed associated hydrogen bond because of the hybrid effect between PVAc and TiO2 sol. Finally, The photooxidative decomposition of methylene blue by using the titania nanomaterials was examined and compared.