The polymerization-induced self-assembly (PISA) of amphiphilic diblock copolymer nano-objects, which are synthesized via reversible addition-fragmentation chain-transfer (RAFT) aqueous polymerization, is discussed. First, the effectiveness of the (S)-2-(ethyl propionate)-(O-ethyl xanthate) as a RAFT chain transfer agent for the polymerization of N,N-dimethylacrylamide (DMAm) yielding a water-soluble macro RAFT agent is investigated. In a second step, poly(DMAm) macro-CTA is chain-extended with acrylate monomers in water inducing a PISA process. Besides the use of pentafluorophenyl acrylate (PFPA) as core-forming block, the thermo-responsive nature of N-isopropylacrylamide (NIPAm) and the reactive character of pentafluorophenyl acrylate (PFPA) for a subsequent post-modification is exploited. Monomer conversion and reaction kinetics are determined via nuclear magnetic resonance spectroscopy, while gel permeation chromatography is used to evaluate the molecular weight distribution of the polymers. The obtained spherical nanostructures are analyzed via dynamic light scattering, scanning electron microscopy, transmission electron microscopy and atomic force microscopy.