A generic and efficient strategy to realize a high effective “intrinsic” single molecular luminescence in the condensed state was proposed by theoretical simulation at the macrostructure level at first, and then was confirmed by molecular design and preparation of a dumbbell-type (H2) and tadpole-type (H1) polyhedral oligomeric silsesquioxane (POSS) based hybrid. The enhancement mechanism of the optical properties was investigated in theory and with experiments. It was found that the incorporation of a “huge” inorganic POSS core on the nanoscale into the organic light-emitting molecules to form three-dimensional (3D) organic–inorganic hybrids effectively improved the optical properties in the condensed matter by decreasing the intermolecular dipole–dipole and π–π stacking interactions owing to the hindrance of the intermolecular charge-transfer between adjacent organic molecules. The dumbbell-type hybrid (H2) showed a better enhancement effect of the optical properties than the resultant tadpole-type hybrid (H1) owing to the crisscross-type arrangement of its dimer induced by the incorporation of POSS. Simultaneously, the two hybrids exhibited high thermal stability and good film forming ability.