A new polybenzoxazole containing an adjacent hydroxyphenyl group was synthesized by using Suzuki coupling reaction accompanied by a simultaneous elimination reaction of acetyl protecting group of hydroxyl group. The polymer in solution as well as in the film exhibited a strong emission (520 nm) with a large Stokes shift (about 200 nm) via excited-state intramolecular proton-transfer mechanism. The new conjugated polymer containing 2-(2'-hydroxyphenyl)benzoxazole exhibited a unique fluorescence quenching property upon UV irradiation. We demonstrate simple yet effective fluorescence imaging on the films of the new polymer by means of UV irradiation without aid of any photoacid generator and postprocessing such as baking or etching. The resulting fluorescence image was stable over 100 days of storage in ambient conditions.