A simple method for nanocrystalline cellulose (NCC)/fluorinated polyacrylate was developed by RAFT-mediated surfactant-free emulsion polymerization, in which the nanocomposites formed a core-shell spherical morphology. The influence of the content of NCC-g-(PAA-b-PHFBA) (AA was acrylic acid, HFBA was hexafluorobutyl acrylate) on the properties of latex and film were systematically studied. The monomer conversion, the tensile strength, and water-oil repellency of film increased first and then decreased, the latex particle size decreased first and then decreased, when the content of NCC-g-(PAA-b-PHFBA) increased from 1 to 6 wt %. Elongation at break and thermal stability distinctly decreased when the content of NCC-g-(PAA-b-PHFBA) gradually increased. XPS showed that the fluorine-containing groups well concentrated at the film-air interfaces during the annealing process. SEM analysis revealed that the treated fiber had a rugged surface, and the treated fabric had an excellent water repellency. In addition, this green grafting method in water offered a new perspective for the fabrication of exceptional NCC-based nanocomposites with NCC as the core and also helped to promote the potential applicability of NCC in a range of multipurpose applications. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1305-1314