Amphiphilic star shaped polymers with poly(ethylene oxide) (PEO) arms and cross‐linked hydrophobic core were synthesized in water via either conventional free radical polymerization (FRP) or atom transfer radical polymerization (ATRP) techniques using a simple “arm‐first” method. In FRP, PEO based macromonomers (MM) were used as arm precursors, which were then cross‐linked by divinylbenzene (DVB) using 2,2′‐azoisobutyronitrile (AIBN). Uniform star polymers ( < 1.2) were achieved through adjustment of the ratio of PEO MM, DVB, and AIBN. While in case of ATRP, both PEO MM, and PEO based macroinitiator (MI) were used as arm precursors with ethylene glycol diacrylate as cross‐linker. Even more uniform star polymers with less contamination by low MW polymers were obtained, as compared to the products synthesized by FRP.
< 1.2) were achieved through adjustment of the ratio of PEO MM, DVB, and AIBN. While in case of ATRP, both PEO MM, and PEO based macroinitiator (MI) were used as arm precursors with ethylene glycol diacrylate as cross‐linker. Even more uniform star polymers with less contamination by low MW polymers were obtained, as compared to the products synthesized by FRP. 