The synthesis by aqueous RAFT polymerization of hydrophilic narrowly dispersed imidazolium-based poly(ionic liquid)s (Đ typically below 1.20) is reported. Full monomer conversion is achieved within hours and high end-group fidelity of the living end groups affords the preparation of well-defined block copolymers. The resulting poly(ionic liquid) macroRAFT agents are finally exploited to polymerize 2-vinylpyridine in water and generate PIL-based nanoparticles of various morphologies (spheres, vesicles, or worms) in a one-pot surfactant-free process.