Two well defined, blue luminescent homopolymers containing 9,9-diethylfluorene core with electron withdrawing pendant pyridine, Suzuki-coupled with the corresponding borolane of decoxy phenyl (PFPA) and naphthalene (PFNA) have been designed and synthesized efficiently. The obtained rod-coil polymers have the average molecular weight of 15212 (PFPA) and 15130 (PFNA) with polydispersity indices (PDIs) 1.07 and 1.3, respectively. The polymers have good solubility and high thermal stability with the decomposition temperature of 362 °C (PFPA) and 367 °C (PFNA) correspondingly. Furthermore the optical and electrochemical properties of the polymers have been investigated. The polymers exhibited photoluminescence (PL) maxima at 410 nm (PFPA) and 414 nm (PFNA) excited at 340 nm, as stable blue luminescence polymers at low concentration of 10−6 M with a quantum yield of 0.64 and 0.62, respectively. In addition the annealed (150 °C) polymer films showed better stability of its photoluminescence spectra. Absorbance and fluorescence emission spectra of PFPA and PFNA were compared in order to evaluate the effects of substituent, phenyl and naphthalene in pyridine pendant fluorene moieties.