Abstract: TPA-functionalized poly(triphenylamine benzobisoxazole) precursor (TPA-PrePBO) was synthesized by polycondensation of 4,6-di(tert-butyldimethylsilylamino)-1,3-di(tert-butyldimethylsiloxy)benzene (TBS-DAR) and 4,4'-diacid chloride triphenylamine, followed by the thermal cyclization reaction, high molecular weight D-A photoelectric material poly(triphenylamine benzobisoxazole)s (TPA-PBO) was successfully prepared for the first time. The precursor TPA-PrePBO has excellent solubility in conventional organic solvents such as N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and dimethylsulfoxide (DMSO). The intrinsic viscosity can reach 1.59 dL/g and the polymer solution can be casted into a flexible and tough film due to the excellent solubility of the TPA-prePBO. The polymer can be conveniently provided in various forms by spin-on or dip-coating processes. The photophysical properties of TPA-PBO was investigated:the maximum UV-visible absorption is at 486 nm, the excitation wavelength of fluorescence is at 553 nm, and the band gap is only 2.20 eV, which is much smaller than those of triphenylamine-polyimide (TPA-PI) and traditional PBO. Moreover, TPA-PBO polymer had high thermal stability and the initial decomposition temperature in the nitrogen atmosphere could reach 527℃, showing great potential to work long hours in harsh and complex environments. These studies demonstrate that TPA-PBO can be a new type of organic optoelectronic material with high stability, low excitation voltage and property of easily process.