In this paper, we confirmed the dearomative addition of tertiary alkyl radicals onto BHT derivatives to form highly congested vicinal quaternary carbons to produce tert-alkylated styrenes in the presence of copper catalyst. Although there are three candidate sites in the reaction of BHT with a radical species, we found that alpha-radical selectively reacted at the ipso position of BHT to produce the corresponding dienone structure. Moreover, heteroatom substituted BHT underwent C-C cleavage coupling reactions with alpha-radicals.