Multifunctional triple-compartment hybrids consisting of Au nanoparticle (NP)@mesoporous silica (mSiO2)@metal-organic framework (MOF) have been successfully synthesized via selective nucleation and growth on the surface of NP@mSiO2 nanostructures. Most importantly, these hybrids possess unique dual independent pores with different pore sizes based on mSiO2 and MOF for loading of larger organic molecules and sieving of smaller organic molecules. Through characterization of the pore properties of both porous materials, triple-compartment hybrids can be employed in sensing materials on the basis of the fluorescence properties of the doped fluorescent molecules within the mSiO2 phase and the molecular sieving effect of MOF. These hybrid nanostructures also show plasmonic properties due to the Au NPs.