Core-shell microparticles with functional multilayer shell walls consisting layers of naphtlialene-labeled polyanion ANp10 and polyviologen (PV) were fabricated through layer-by-layer (LbL) self-assembly. Fluorescence emission from the naphthyl group in the ANp10 layer was found to be quenched by the viologen group in the PV layer regardless in inner or outer layer. This quenching was attributed to electron transfer from the excited naphthyl donor to the viologen acceptor. The quenching efficiency was simply tuned by changing numbers of the ALG/CHI bilayer spacer and PV layer. The resulting core-shell microparticles will be served as a novel light-harvesting antenna system. [GRAPHICS] sulted in well-defined PMMA. [GRAPHICS] in situ reduction, a large number of metal-based functional materials can be prepared. PVP is alkaline, and thus capable of catalyzing the sol-gel process to generate an inorganic shell. Furthermore, pre-formed nanoparticles can also be absorbed by the shell through specific interactions. The PS core is not infiltrative during synthesis, and hollow rings can be derived after the polymer templates are removed. [GRAPHICS] b