The electrospun nanofibers emerge several advantages because of extremely high specific surface area and small pore size. This work studies the effect of PVA nanofibers diameter and nano-sized TiO2 on optical properties as reflectivity of light and color of a nanostructure assembly consisting polyvinyl alcohol and titanium dioxide (PVA/TiO2) composite nanofibers prepared by electrospinning technique. The PVA/TiO2 composite spinning solution was prepared through incorporation of TiO2 nanoparticles as inorganic optical filler in polyvinyl alcohol (PVA) solution as an organic substrate using the ultrasonication method. The morphological and optical properties of collected composites nanofibers were highlighted using scanning electron microscopy (SEM) and reflective spectrophotometer (RS). The reflectance spectra indicated the less reflectance and lightness of composite with higher nanofiber diameter. Also, the reflectance and lightness of nanofibers decreased with increasing nano-TiO2 concentration. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013