The synthesis of primary amine end-functional poly(tert-butyl acrylate)s has been achieved by using the Gabriel reaction. Polymerization of tert-butyl acrylate was first achieved by atom transfer radical polymerization using ethyl-2-bromoisobutyrate or paramethoxyphenyl-2-bromoisobutyrate as initiator. Both resulting polymers, with a bromide-end atom, were converted into phthalimido intermediates which then were successfully hydrolyzed using potassium hydroxide in tert-butyl alcohol to result ID in poly(tert-butyl acryl-ate)s terminated by a primary amine function. End group interconversions were followed by H-1 NMR, FT-IR, and MALDI-TOF MS measurements. All the results proved that quantitative transformations were achieved at each step. Moreover, the method developed is very easy to carry out.