Novel　luminescent　dense　nano-silica　hybrid　materials　(DNSS)　modified　with　different　amounts　of　(3-aminopropyl)triethoxysilane　(APTES)　and　1,8-naphthalic　anhydride　(NA)　were　successfully　synthesized　via　two　steps　combined　with　post-grafting　methods.　Powder　X-ray　diffraction　(XRD),　N-2-sorption　analysis,　Fourier　transform　infrared　(FT-IR)　spectroscopy,　transmission　electron　microscopy　(TEM),　thermogravimetric　analysis　(TGA),　photoluminescence　(PL)　spectroscopy　and　elemental　analysis,　as　well　as　time-resolved　decays　were　employed　to　characterize　the　resultant　hybrid　materials.　The　results　revealed　that　luminescent　organic　molecules　had　been　successfully　loaded　onto　the　amine-modified　surface　of　nano-silica　spheres.　In　addition,　their　fluorescence　intensity　and　characteristic　peak　of　emission　spectra　changed　with　increasing　amount　of　APTES　and　NA　additive.　In　particular,　the　characteristic　peak　showed　a　red　shift　from　390　to　450　nm,　however,　this　was　inconsistent　with　results　calculated　on　the　basis　of　the　elemental　analysis　data,　most　probably　because　of　the　dispersion　behaviors　of　NA　molecules　from　the　aggregating　to　the　monolayer　state.　These　observations　demonstrated　the　existence　of　a　quantum　confinement　effectiveness　of　NA-DNSS　samples,　and　therefore　a　possible　mechanism　was　put　forward.　Copyright　(c)　2013　John　Wiley　&　Sons,　Ltd.