New ladder-type p-conjugated polymer poly{6-alkyl-pyrrolo[3,2-b:4,5-b']bis-[1,4]benzothiazine} (PPBBTZ) was synthesized through a simple method. PPBBTZ showed good solubility in organic solvents (such as chloroform, tetrahydrofuran, chlorobenzene, o-dichlorobenzene) and high thermal stability (decomposition temperatures up to 323 degrees C and 299 degrees C in nitrogen and air, respectively). The highest occupied molecular orbital and lowest unoccupied molecular orbital energy level estimated from electrochemistry result and absorption spectrum were -5.46 and -3.81 eV, respectively, with a band gap of 1.65 eV. More interestingly, PPBBTZ displayed broad absorption from ultraviolet to visible light regions (200750 nm). These properties suggested PPBBTZ was a good candidate in opto-electronics. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012