In this study, monodispersed silica spheres were successfully synthesized by seed-growth method and they can be highly dispersed in the poly(vinyl alcohol)(PVA) solution. PVA/silica composite fibers were fabricated by electrospinning the composite solutions containing different amount of silica. Further investigation showed that the size distribution of silica sphere was monodispersed and the spheres were homogeneously dispersed in the fibers individually. The composite fibers showed an uniform and continuous morphology with a average diameter of 298-345 nm. The as-spun nanofibers were characterized by Field Emission Scanning Electron Microscope. (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). POLYM. COMPOS., 32:347-352, 2011. (C) 2011 Society of Plastics Engineers