The first novel polyfluorene copolymers containing siloxane bridges were synthesized by Ni(0)-mediated copolymerization between 2,7-dibromo-9,9‘-dihexylfluorene and a bridged fluorene monomer containing siloxane linkages. Two such bridged copolymers were prepared: PSiloBg1 (containing 1 mol % siloxane-bridged fluorene unit) and PSiloBg3 (containing 3 mol % siloxane-bridged fluorene unit). PSiloBg1 and PSiloBg3 exhibited good solubility in common organic solvents, thermal stability up to 420 °C, and facile film formation. The glass transition temperatures of the bridged polymers (106 and 110 °C, respectively) were higher than that of the homo poly(dihexylfluorene) (PDHF). In particular, PSiloBg3 exhibited a polymerization yield (96%) and a molecular weight (MW = 185 000) higher than those of PDHF (polymerization yield = 62%, MW = 82 000). Interestingly, after the bridged polymers had been annealed at 150 °C for 4 h in air, their PL spectra showed no significant increase in vibronic structures at 450 and 4...