5,8-Dibromo-13,13-bis(alkyl)dibenzofluorene derivatives functionalized with different alkyl mols. [M2a-M2f] and 2-tert butyl-9,10-di (p-hydroxyphenyl) anthracene [M1b], were designed to research the impact of mol. structure on the optical properties of polymer. Polymers were synthesized by aromatic nucleophilic substitution in moderate to strong yields (60-65%). After structural characterization through several techniques (e.g. FTIR, 1H, and 13C-NMR), special emphasis was put on the study of their optical properties through UV-Vis and photoluminescence spectroscopy. The polymers demonstrated strong thermal stability up to 350 °C and high glass transition temperature (108-133 °C). All of the polymers showed blue emission within a range of 416-433 nm and had a band gap of 2.87-2.99 eV. The electrochem. study reveals that, HOMO levels for polymers were estimated in the range of - 5.22 to - 5.26 eV and LUMO of - 2.23 to - 2.38 eV. The polymers demonstrated strong thermal stability and blue emission within a range of 416-433 nm. These polymeric materials have demonstrated high photoluminescence which may be useful for future display applications as a good source.