4,4\'-dibromo-2-nitro-biphenyl and 4,4\'-dibromo-2,3\'-dinitro-biphenyl have been synthesized via nitration reaction with 4,4′-dibromobiphenyl as the raw material. Three novel thiophene derivatives, 4, 4′-di(4-hexyl-thiophen-2-yl)biphenyl, 4,4′-di(4-hexyl-thiophen-2-yl)-2- nitro-biphenyl and 4,4′-di(4-hexyl-thiophen-2-yl)-2,3\'-dinitrobiphenyl were synthesized through Stille coupling reaction, followed by polymerization in the presence of FeCl3, respectively. UV-vis absorption spectra, fluorescence spectra, photoluminescence spectra and electrochemical properties of the polymers were investigated. And the band-gap (Eg), HOMO orbital energy (EHOMO), and LUMO orbital energy (ELUMO) of the polymers were calculated. Among the polymers, polymer PBTN and PBTD show lower band-gap (2.67 and 2.63 eV), lower HOMO energy level (-5.38 and -5.4 eV) and broader wavelength (432 and 438 nm) than that of polymer PBTB (2.69 eV, -5.36 eV and 424 nm) with incorporation of one nitro group or two nitro groups in the main chain, respectively.