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Four different types of alternating copolymers, named as poly(N-(2-ethylhexyl)-3,6-dibromo-carbazole-alt-aniline) (P1), poly(3,6-dibromo-carbazole-alt-aniline) (P2), poly(N-(3,5-dibromo-methylene-phenyl)-carbazole-alt-aniline) (P3) and poly(N-[4-(2-ethylhexyloxyl)-3,5-dibromomethylene-phenyl]-carbazole-alt-aniline) (P4) were successfully synthesized by palladium-catalyzed polycondensation of corresponding carbazole-containing dibrominated compounds and an aniline. These resulting polymers exhibited good solubility in normal organic solvents and showed relatively high molecular weights. Excellent thermal stability of the polymers was observed from TGA, showing less than 8% of weight loss on heating to 350°C under N₂ atmosphere. From UV-Vis absorption and photoluminescence spectra of these solution-processable polymers, it was observed that λ_max,UV was in the range of 308 – 352 nm and λ_max,PL was in the blue emission range of 450 – 463 nm. Electrochemical characteristics of these alternating copolymers were investigated to prove the potential in application for blue-emitting host matrix and hole-transporting layer in polymer light-emitting devices.