Di-polyethylenyl magnesium compounds, obtained by a transition metal catalyzed chain growth reaction on butyloctyl magnesium, are reacted with a range of disulfides of thiocarbonylated compounds (RC(S)SSC(S)R). Xanthate, dithiocarbamate, dithloester, and trithiocarbonate-functionalized polyethylenes are thus obtained and characterized by H-1 NMR and IR spectroscopy, and MALDI TOF mass spectrometry. These macroRAFT agents may serve as building blocks for the synthesis of block copolymers based on polyolefins and polar segments.