A new hybrid photostable donor–acceptor mesoporous SBA-15 silica system was designed and prepared. It consists of an encapsulated donor, the Super Yellow (SY) polymer, which transfers the photoexcitation energy directly to an acceptor dye that is linked outside the framework. The obtained composite material was characterized by X-ray diffraction, nitrogen-physisorption porosimetry, diffuse-reflectance (DR)-UV/Vis spectroscopy and photoluminescence, space- and time-resolved confocal microscopy. The physico-chemical analyses showed that the system behaves as an efficient Förster resonance energy transfer (FRET) pair, and high photoluminescence was observed from the acceptor. The presented photonic antenna is the first example of dye sensitization by polymer-loaded mesoporous silica and represents a step forward in the search for new efficient and stable materials with opto-electronic applications.