Using γ-radiation as initiation source at ambient temperatures (i.e. T~20 o C) for reversible addition-fragmentation chain transfer (RAFT) polymerizations allows for the generation of narrowly distributed polymeric material with living characteristics. It is shown that the living characteristics effected by RAFT agent mediated bulk polymerizations using γ-irradiation are associated with a RAFT mechanism rather than with reversible termination processes. Furthermore, γ-radiation as initiation source for an appropriate RAFT agent/monomer system allows for effective radical storage and the generation of long-lived reaction intermediates at ambient temperatures.The current overview further demonstrates how the RAFT process together with γ-radiation as source of initiation can be employed to graft various monomers onto polypropylene surfaces in a controlled manner.