This review summarizes our achievements in designing new initiation systems for atom transfer radical polymerization (ATRP). First-order kinetics and extension experiments revealed the living nature of these reactions. Tailor-made vinyl polymers with functional end groups were characterized by 1H-NMR and UV-vis spectroscopic analyses.Replacing traditional radical initiators AIBN and BPO

carbon-carbon bond compounds

1

1

2

2-tetraphenyl-1

2-ethanediol

diethyl 2

3-dicyano-2

3-diphenylsuccinate and diethyl 2

3-dicyano-2

3-di(p-tolyl)succinate

were utilized in reverse ATRP to produce the initiating radical. Sulfur-sulfur bond iniferter

tetraethylthiuram disulfide (TD)

in conjunction with CuBr/bpy or NiCl2/PPh3 complex could control the styrene polymerization via redox reaction. Pseudo-halogen transfer reaction was demonstrated to maintain the dormant-active species equilibrium in normal and reverse ATRP with xu(S2CNEt2)

Cu(S2CNEt2)Cl and xe(S2CNEt2)3 as catalysts. The organic halide initiator and reduced transition metal compound that started the living polymerization were produced in situ from the components of TD/FeCl3/PPh3

TD/CuBr2/bpy and Fe(S2CNEt2)3/FeCl3/PPh3 systems. Accurate control of UV irradiation time favored the radical generation process in photo ATRP with the 2

2-dimethoxy-2-phenylacetophenone/Fe(S2CNEt2)3 initiation system.