Electrostatic interactions between the zeolite cavity and confined noble-metal nanoparticles govern the photophysical properties of these materials. A better understanding of these interactions can afford new perspectives in optoelectronics applications. We investigated this interplay by revealing the peculiar photophysical properties of Ag clusters embedded in nanosized faujasite zeolite structures. Crystal size and steady state optical properties were characterized via integrated light and electron microscopy (ILEM) and steady state spectroscopy. Extensive time-resolved spectroscopy experiments performed on femtosecond to millisecond time scales revealed excited state dynamics that are intriguingly different from those observed for their micrometer sized counterpart. Multiscale modeling investigations were performed to rationalize the effect of the crystal size on the photophysical properties. Our results indicate that for the nanosized crystals, the emissive properties as well as the radiative and nonradiative processes involving the Ag clusters are dramatically dependent on the surface charge density and surface charge balance.