A　new　electrochemical　strategy　for　the　atom　transfer　radical　addition　(ATRA)　of　polychloroalkanes　across　olefins　has　been　realized　by　the　synergism　of　paired　electrolysis　and　halogen　bonding　activation.　Notably,　readily　accessible　4,4-di-tert-butyl　bipyridine　(dtbpy),　acting　as　a　halogen　bonding　acceptor,　shifted　the　reduction　potential　of　C-Cl　bonds　positively　by　110　mV.　The　decreased　operating　potential　leads　to　a　wide　substrate　scope　and　excellent　functional　group　compatibility.　A　diverse　array　of　terminal　and　internal　alkenes　such　as　(hetero)aryl　olefins,　unactive　aliphatic　olefins,　and　natural　products　and　drugs-derived　olefins　were　well　compatible.