In this communication we report the synthesis and the efficient polymerization of a PPV trimer, 4-tert-butyl-4'-(4-vinylstyryl)-trans-stilbene. By using the TEMPO (2,2,6,6-tetramethylpiperidin-1-yloxy)-mediated free-radical polymerization method, the corresponding polymer was obtained in high yields, with a fair molecular weight and a small polydispersity. The presence of phenylenevinylene units in the side chains of the polymer gives rise to efficient blue fluorescence which makes the material suitable for light emission applications.