Nanostructured fluorescent pyrromethene (PM) doped-silica core-shell particles were successfully prepared by Stöber process. The average size of the particles was in the range of 10–20 nm measured by TEM micrograph. The atomic structure and morphology of PM 597/SiO2core/shell nanoparticles were studied by AFM and SEM, respectively. Absorption and emission spectra of the PM 597/SiO2core/shell nanoparticles under the UV irradiation were studied and not significantly influenced at the position of peaks. Finally, amplified spontaneous emission (ASE) and photobleaching of dye were examined and found no significant influence on the peaks of PM dye due to the formation of smaller sizes of PM 597/SiO2core/shell nanoparticles. The observed PM 597/SiO2core/shell nanoparticles were different in shapes with smaller size distribution and highly luminescent. Majority of nanoparticles were roughly spherical with many of them aggregated. The less photobleaching of dye core may be due to the protection of pumped energy by SiO2shell and restricts the leakage of dye.