We have synthesized two fluorene-based polymeric host materials, P1 and P2, through palladiumcatalyzed Suzuki couplings of monomers containing tetraphenylsilane and 3,6-disubstituted fluorene frameworks, respectively. The resultant copolymers exhibited high glass transition temperatures (T g g 215°C) and excellent thermal stability. The conjugation lengths of polymers P1 and P2 were effectively confined through the presence of the 3,6-linkages and silane units in the polymer skeleton. The structural features endowed these copolymers with UV-violet emissions in the solid state, together with high triplet energies (E T ) 2.60 eV), which were sufficiently high for P1 and P2 to serve as appropriate hosts for green-emitting phosphors. In the case of polymer P2, the incorporation of pendent carbazole groups increased the HOMO level markedly and balanced the rates of charge injection and transportation. Employing P2 doped with green-emitting fac-tris(2-phenylpyridine)iridium as the emissive layer, we fabricated highly efficient polymer light-emitting diodes (32 cd/A, 9.2%) that exhibited significantly enhanced EL performance relative to that of the system employing P1 (14.5 cd/A, 4.2%).