The free radical polymerization of 4-vinylpyridine (4VP), using 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) radical as a capping agent, proved to proceed in a pseudo-living manner, providing low polydispersity P4VP whose chain growth could be controlled. The original nitroxide concentration was revealed to have no obvious influence on the rate of polymerization, whereas it could be directly related to the molecular weight of the polymer. The polydispersity was shown to increase within the range 1.02-1.50. The influence of temperature on the kinetics of the reaction was demonstrated, but no significant effect could be found on the molecular weights and polydispersities of the macromolecules.