Thermally stable and solution-processable poly(N-arylcarbazole-alt-aniline) copolymers with high structural integrity were synthesized in good yields via palladium-catalyzed polycondensation of aniline with corresponding N-arylcarbazole monomers such as N-(2-ethylhexyloxyphenyl)-3,6-dibromocarbazole, bis[6-bromo-N-(2-ethylhexyloxyphenyl)carbazole-3-yl] and N-(4-(2-ethylhexyl)-3,5-dibromomethylene-phenyl)carbazole, respectively. The optical and electrochemical properties of these copolymers were measured and compared with those of poly(N-alkylcarbazole-alt-aniline) copolymer. All synthesized poly(N-arylcarbazole-alt-aniline) copolymers showed maximum UV-Vis absorption peaks at around 300 nm in THF solution, and exhibited maximum photoluminescence peaks in the blue emission range from 430 to 460 nm. It was also found that poly(N-arylcarbazole-alt-aniline) copolymers had wider band gap energy than poly(N-alkylcarbazole-alt-aniline) copolymer.