A new POSS (polyhedral oligomeric silsesquioxane)-substituted polyfluorene was synthesized from the nickel-catalyzed Yamamoto coupling reaction. The synthesized polymers could be well characterized by H-1 NMR, FT-IR, and elemental analysis. PL spectra of PFPOSSs on the quartz film showed reduced aggregation/excimer formation because the bulky POSS group prohibited interchain interactions. This effective dilution effect and the high thermal stability of the POSS unit also improved the color stability of PFPOSSs blue emission even after thermal annealing at 150 degreesC. The fluorescence quantum yields (Phi(FL)) of PFPOSSs in both solution and solid state were higher than those of poly(dialkylfluorene)s. Moreover, the ITO/PEDOT-PSS/polymer/Ca/Al LED device using this polymer as emitting layer showed a very stable blue light emission. LED devices of PFPOSSs showed a low turn-on voltage of 3.7-4.4 V, high brightness of 350-1010 cd/m(2), and external efficiencies of 0.11-0.36%.