The combination of RAFT chemistry and the hetero-Diels-Alder (HDA) cycloaddition was successfully utilized in the synthesis of poly(styrene) (PS) star polymers with up to 4 arms. This variant of the coupling onto method of star polymer synthesis was investigated for two different RAFT end groups (diethoxyphosphoryldithioformate and pyridin-2-yldithioformate) and coupling agents bearing 2, 3, or 4 diene functional groups. When a diethoxyphosphoryldithioformate terminated polymer was reacted with the 2-, 3-, and 4-fold functionalized coupling agents, the yields of 2-arm star, 3-arm star, and 4-arm star polymers were 81 , 77 , and 65 , respectively, and when a pyridin-2-yldithioformate terminated polymer was reacted with the same coupling agents, the yields of 2-arm star, 3-arm star and 4-arm star polymers were 91 , 86 and 82 respectively. The HDA coupling reaction was monitored via UV/vis spectroscopy from the perspective of the RAFT end group as well as by 1H NMR spectroscopy from the perspective of the diene functionality. The results of these investigations indicated that the phosphoryldiethoxydithioformate terminated polymer achieves 92 conversion within a 24 h time frame and the pyridin-2-yldithioformate terminated polymer achieves 96 conversion in 10 h. The 4-arm star polymers were also subjected to high-temperature environments, and GPC measurements indicated that complete cleavage of all 4 arms from the core was achieved in 24 h at 160 ?C.