The spontaneous emission of light from light-emitting materials adsorbed within the ordered pores of monodispersed mesoporous silica spheres (MMSS) has been investigated. By taking advantage of the ordered starburst pores of MMSS, we can provide a simple strategy for fabricating synthetic opals consisting of homogeneous individual building blocks in which fluorescent guests are uniformly and stably impregnated. In this study, tris(8-hydroxyquinolinato)aluminum(III) (Alq(3)) and Rhodamine B (Rh B) are selected as the fluorescent guests. The former has a wider emission band than the reflection spectrum of MMSS synthetic opals, whereas the emission band of the latter is considerably narrower than the reflection spectrum of the opals. The spontaneous emissions of these functionalized synthetic opals are clearly influenced by the stop band governed by the Bragg equation. In the case of the Alq(3)-MMSS conjugate, the shape of the Alq3 emission spectrum varies in accordance with the shift in the stop band. The emission of the Rh B-MMSS conjugate is noticeably narrowed, and its intensity is enhanced when the excitation intensity is increased. These results are well explained by an inhibition of spontaneous emission caused by a reduction in the density of optical states within the stop band. The results of this study indicate that MMSS synthetic opals are promising For use in novel optical applications in 4 which the spontaneous emission can be manipulated.