A hyper branched 10-butylphenothiazine with in-situ thermally curable methacrylate (1,3,5-tris-[{10-Butyl-3-(4-(2-methyl-acryloyloxy)-phenyl)-7-yl-10H-phenothiazine}]-benzene, (tris-PTMA)) was synthesized successfully. From the TGA thermogram of tris-PTMA was thermally stable up to 336 oC. In the first heating scan of DSC thermogram, tris-PTMA showed glass transition temperature (Tg) at 140 oC and broad endothermic process in the region of 144-179 oC, which is thermally curing temperature. In the second heating process, Tg exhibited at 158.7 oC and endothermic process was not observed. Thermally cured tris-PTMA showed no big change in the UV-visible spectrum after washing with organic solvent such as methylene chloride, chloroform, toluene, indicating that thermally cured film was very good solvent resistance. Thermally cured tris-PTMA was electrochemically stable and the HOMO energy level of tris-PTMA was .5.54 eV. The maximum luminance efficiency of double layer structured polymer light-emitting diode based on in-situ thermally cured tris-PTMA was 0.685 cd/A at 16.0 V, which was higher than that of the device without thermally cured tris-PTMA (0.348 cd/A at 15.0 V).