Self-assembled SnO2 nanoparticles embedded in a poly(4-vinylphenol) (PVP) polymer layer were formed by using spin coating. X-ray photoelectron spectroscopy spectra showed that Sn 3d and O is peaks corresponding to the SnO2 nanoparticles appeared, indicative of the formation of SnO2 nanoparticles. Bright-field transmission electron microscopy image and selected area electron diffraction patterns showed that the SnO2 nanoparticles were randomly distributed in the PVP layer. Photoluminescence spectra for the synthesized SnO2 nanoparticles in a dibutyl ether solution showed that the dominant exciton peak corresponded to the band-edge emission was observed.