Photocontrolled iodine-mediated reversible-deactivation radical polymerization (RDRP) is a facile and highly efficient access to precision polymers. Herein, a facile photocontrolled iodine-mediated green RDRP strategy was successfully established in water by using 2-iodo-2-methylpropionitrile (CP-I) as the initiator and water-soluble functional monomers including poly(ethylene glycol) methyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), and 2-hydroxypropyl methacrylate (HPMA) as the model monomers under blue-light-emitting diode (LED) irradiation at room temperature. Well-defined polymers (PPEGMA, PHEMA, PHPMA) with narrow polydispersities (1.09-1.21) were obtained, and amphiphilic block copolymers which can form nanospheres in situ in water (PPEGMA-b-poly(benzyl methacrylate) (PPEGMA-b-PBnMA) and PPEGMA-b-PHPMA) were prepared. To explore the role of water in our polymerization, control experiments were successfully carried out by using oil-soluble monomer methyl methacrylate (MMA) with the help of trace amounts of water. Notably, the green solvent-water-has an additionally positive effect in accelerating the polymerization and makes our polymerization system an environmentally friendly polymerization system. Therefore, this simple strategy conducted in the presence of water enables the green preparation of well-defined water-soluble or water-insoluble polymers and clean synthesis of amphiphilic copolymer nanoparticles in situ.