Here, the synthesis of triblock terpolymers using tert-butyl acrylate, glycidyl methacrylate, and methyl methacrylate was studied in detail using atom transfer radical polymerization. Those polymers are promising candidates for irreversible linked microstructured layers on surfaces. The experiments showed that the polymerization has to be started with the acrylate and can be extended with the methacrylates. The first two steps can be done in a one pot procedure employing the method of halogen exchange. With optimized reaction conditions in the last step, the obtained terpolymers show narrow molecular weight distributions and the polymerization process is well controlled. Conducting the synthesis in the opposite direction mostly a nonuniform product was obtained as the GPC analysis showed. Further characterization was done with H-1 NMR spectroscopy, thermogravimetric analysis, and differential scanning calorimetry, the latter showing different glass points for the single blocks in the terpolymers if they are not too short. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 675-684