In order to disperse luminescent compounds with low solubility or high crystallinity into silica matrices, we demonstrate here facile one-pot synthesis of organic-inorganic luminescent hybrids via simultaneous process of sol-gel reaction of 3-(chloropropyl)trimethoxysilane (CPTMS) and the Suzuki-Miyaura homocoupling of 1-pyreneboronic acid under microwave irradiation. Highly luminescent hybrid without aggregates of the pyrene dimer, which was efficiently generated in situ, was obtained by microwave irradiation due to rapid formation of silica matrices, whereas huge aggregates were observed in the hybrid prepared under conventional heating.