In this study, block copolymers poly(methyl methacrylate-b-styrene) and poly(methyl methacrylate-b-acrylamide) were synthesized in two steps using a combination of the redox polymerization method and the atom transfer radical polymerization (ATRP) method. For this purpose, polymethyl methacrylate (PMMA-Br macroinitiator) was synthesized by redox polymerization of methyl methacrylate (MMA) and 3-bromo-1-propanol. Ce(NH4)(2)(NO3)(6) was used as a catalyst for the redox polymerization. The syntheses of poly(MMA-b-S) and poly(MMA-b-AAm) block copolymers were carried out by means of ATRP of PMMA-Br macroinitiator, styrene (S), and acrylamide (AAm) at 110 degrees C. The block length of the block copolymers was adjusted by changing various parameters such as monomer and initiator concentrations. The characterization of the products was achieved using multi-instruments and methods such as nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, and fractional precipitation [solvent (THF-mL)/nonsolvent (petroleum ether-mL)] techniques.