A novel blue‐light emitting terphenyl‐bridged ladder polysiloxane ( TBLP) was prepared by the condensation of a tetrasilanol monomer via a ladder supramolecular structure. TBLPs emit narrow blue light (420 nm) with high quantum yields (0.96) in diluted solution and shows no evident fluorophore aggregation in the solid state, indicating that the terphenyls are well isolated due to confinement of the ladder‐rungs. In addition, it has excellent emission stability at high temperature based on TGA, DSC and annealing experiments. Overall, TBLPs can be considered as a potential material for fabricating stable and high‐efficiency blue‐light emitting optoelectronic devices.
