Electrochemically mediated atom transfer radical polymerization (eATRP) of acrylamide was investigated in aqueous media. The synthesis of poly(ethylene oxide)-block-poly(acrylamide) block copolymers via eATRP under potentiostatic conditions was carried out. Various polymerization parameters were examined, including temperature, monomer concentration, ligand structure, and degree of polymerization (DP). Under optimized reaction conditions, the DP of resulting copolymers increased linearly with monomer conversion and semilogarithmic kinetic plots were linear. Successful chain extension and formation of the block copolymers confirmed the living nature of the eATRP of acrylamides in aqueous media.