The scientific research achievement of“RAFT polymerization of 2-vinylpyridine at ambient temperature” is designed for the comprehensive experiment of polymer chemistry. The RAFT of 2-vinylpyridine with S-1-dodecyl-S-(α, α-dimethyl-α-aceticacid) trithiocarbonate (DDMAT) as chain transfer agent without a reductive initiator has been proceeded with in the presence of an oxidation mesothermal initiator only, i.e., benzoyl peroxide. The results showed that RAFT polymerization of 2-vinylpyridine could be carried out easily at room temperature; the structure of the prepared Poly (2-vinylpyridine) could be controlled with narrow molecular weight distribution (PDI< 1.20). The experiment can help students to master basic experimental techniques of synthetic polymer, master skills of operating large instrument, broaden students’academic horizons, and improve their practical and innovative abilities.