The pure polyvinyl acetate (PVAc) nanofiber and PVAc/titanium dioxide (TiO2) composite nanofiber were prepared by sol-gel process with electrospinning. The effect of increasing TiO2 contents on diameter distribution, surface morphology, and elastic modulus of nanofibers was characterized using a scanning electron microscope (SEM) and an atomic force microscope (AFM) equipped with picoforce. SEM images showed that the average diameter of composite nanofiber decreased with the increase in TiO2. The three-point bending test indicated that the elastic modulus of PVAc/TiO2 nanofiber significantly increased as TiO2 increased.