AbstractThe functionalization and application of nano‐objects generated using a polymerization induced self‐assembly (PISA) procedure is becoming a focus in recent years. In this contribution, using ethanol as solvent, poly(oligo(ethylene oxide) methyl ether methacrylate) (POEOMA) as macro‐initiator/stabilizer, and 2‐(perfluorohexyl)ethyl methacrylate (PFHEMA) and glycidyl methacrylate (GMA) as comonomers, the initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP)‐based PISA is realized. The lower GMA content system tends to form spheres with large diameters and heavy contrast, while the lower PFHEMA content system tends to form the spheres or short worms with small diameters. However, the system with further increased GMA content results in the failed ICAR ATRP PISA procedure with the formation of precipitates by the cross‐linking reaction between pendant epoxy groups. Furthermore, using the efficient reaction between the epoxy group on GMA and thiol group on mercapto‐succinic acid agent, the carboxyl groups can be introduced into the inner cavity of the nano‐objects and used for incorporation with the Fe2+ and Fe3+ ions, and the organic–inorganic nanoparticles Fe3O4@POEOMA are finally prepared in the presence of a reductant.