In this work, we demonstrate that optical resonators built using all-nanoparticle-based porous building blocks provide a responsive multifunctional matrix, totally different emission spectra being attained from the same embedded luminescent nanophosphors under varying environmental conditions. We show a clear correlation between modifications in the ambient surroundings, the induced changes of the resonant modes, and the resulting variations in the emission response. The method is versatile and allows nanophosphors of arbitrary shape to be integrated in the cavity. By precise control of the spectral features of the optical resonances, luminescence is strongly modulated in selected and tuneable wavelength ranges. Applications in the fields of sensing and detection are foreseen for these materials.