The azoalkaneperester tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate (7) has been found to be a viable bifunctional free radical initiator. Unlike the radicals from previously studied compounds 4-6, those from 7 neither fragment nor cyclize, presumably on account of the medium ring that would be required. Thermolysis of 7 with styrene affords macroinitiator 21 while photolysis affords 22. Photolysis of 21 with MMA yields block copolymer 23 while thermolysis of 22 with MMA affords block copolymer 24. One advantage of 7 is that the photolysis-thermolysis sequence can be reversed, as can the order of addition of monomers.