A series of aromatic polyazomethines (PAMs) were prepared via the direct polycondensation from 9-(2-ethylhexyl)-carbazole-3, 6-dicarboxaldehyde and six different kinds of diamine containing triarylamines. The PAMs displayed good solubility in many organic solvents such as tetrahydrofuran (THF), chloroform (CHCl 3 ), N,N-dimethylformamide (DMF), et al which was beneficial for polymer film formation via spin coating, and exhibited outstanding thermal stability.These PAMs exhibited blue-green photoluminescence around 405-520 nm with quantum yield up to 48 % in dichloromethane (CH 2 Cl 2 ) solution. They exhibited halochromic properties with color changing from yellow to red, and accompanied by fluorescence quenching after HCl-doped. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of these PAMs were determined from cyclic voltammograms as -5.01 to -4.88 eV and -2.15 to -2.11 eV, respectively. The PAMs films not only had good electrochromic properties with high coloration efficiency, but also generated photovoltagic and photocurrent under simulated solar radiation.