Combination of vinyl carbazole and thiophene groups’ excellent thermal properties and optical properties, a novel polymer named poly(2,7-bi-2-thienyl-9-vinyl-9-H-carbazole) was synthesized via radical polymerization and Suzuki reaction. The polymer was characterized using Fourier transform infrared spectrometer(FT-IR), gel permeation chromatography(GPC), differential scanning calorimetry(DSC), and X-Ray fluorescence spectrometer(XRF). It was found that this π-conjugated polymer containing vinyl carbazole and thiophene groups gave a high glass transition temperature (Tg=251°C). This feature made poly(2,7-bi-2-thienyl-9-vinyl-9-H-carbazole) possessing an excellent thermal performance.