Bulk free-radical polymerization of 2-vinylpyridine (2VP) in the presence of 2,2,6,6-tetramethylpiperidine-N-oxyl, (TEMPO) was studied under different conditions (temperature and presence of additives). Linear poly-(2-vinylpyridine) with a narrow molecular weight distribution and controllable molecular weight was prepared in the presence of acetic anhydride at 95 degreesC up to a conversion of 66%. At higher conversions side reactions became very important (pseudoliving polymerization). By applying this procedure, well-defined random copolymers of 2VP with styrene or tert-butylmethacrylate as well as block copolymers of 2VP with styrene were synthesized.