Series of light emitting polymers based on dibenzofluorene-acene have been synthesized through aromatic nucleophilic substitution reaction. The polymer displayed strong solubility in specific organic solvents with a polydispersity index of 1.5–2.0 and weight average molecular weight within the range from 25000 to 34000. At 420 nm the highest photoluminescence of the polymer solution was observed. The temperature of the thermal decomposition was determined by TGA and ranged from 300 to 446 ?C while the value of Tg was between 120 and 140 ?C. Cyclic voltammetry tests of polydibezofluorenes show that the compounds with HOMO and LUMO in the range 2.23–5.26 eV is stable under redox condition. The optical properties of these polydibenzofluorenes showed significant blue emissions in the polymers obtained.