Controlled polymerization of styrene was carried out using ambient temperature single electron transfer initiation and propagation through the radical addition fragmentation chain transfer (SET-RAFT) method. SET-RAFT method was expected to have much wider applicability, especially for monomers that polymerize very rapidly by free/living radical polymerization. The typical RAFT polymerization required thermal/photochemical initiation and one of the end groups was required to be a fragment from the initiator. Under the SET-RAFT conditions, the ambient temperature initiation and the use of functional initiators would overcome some of the limitations of RAFT. SET-RAFT condition is expected to be very effective for monomers with a slower rate of initiation compared to the rate of propagation and those with a very high rate of propagation that require control.