Nitroxide-mediated polymerization (NMP) of 2-(diethylamino)ethyl methacrylate (DEAEMA) with a small amount of acrylonitrile (AN) as a comonomer was performed for the first time in water at 90 degrees C and atmospheric pressure using n-hydroxysuccinimidyl BlocBuilder (NHS-BB) alkoxyamine without addition of excess nitroxide. The same reaction was carried out using the bicomponent initiating system composed of 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (VA-044) as initiator and N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) nitroxide (SG1) as nitroxide. Both polymerization reactions were well-controlled and exhibited excellent livingness as evidenced by low molar dispersity and evolution of the molar mass distribution. The hydrolytic stability of DEAEMA at the polymerization conditions and the effects of several parameters including initiating system, temperature, ratio of nitroxide to initiator, initiator and monomer concentrations, and comonomer type were investigated. Chain extension of the synthesized macroinitiator with methyl methacrylate (MMA) and styrene (S) in a one-pot process led to the in situ formation of poly(DEAEMA-co-S)-b-poly(MMA-co-S) diblock copolymers based on the polymerization-induced self-assembly (PISA) process.