In this work, fluorescent silica nanoparticles (FNPs) and their nanocomposites are prepared.Rhodamine B (RhB) molecules, the photosensitive materials, are allowed to bond to silica nanoparticles by means of covalent bonding.FNPs show different photoluminescent (PL) behaviors in THF solution compared to neat RhB moelcules.FNPs dsiplay yellow and blue emissions, hence resulting in a white-light emission.Moreover, FNPs have good compatibility with organic solvents and consequnetly are able to be used as inorganic additives for preparation of photoluminescent polymer-silica nanocomposites.Photoluminescent electrospun nanofibers and hybrid thin films of poly(methylmethacrylate) and FNPs are prepared.The nanocomposites exhibits similar PL behaviors as do FNPs.