Tetrakis(4-(1-bromoethyl)phenyl) silane is synthesized and utilized to initiate the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) to generate bromo-terminated four-armed PMMA macroinitiators, which further initiate the ATRP of methylacryloyloxyl-2-hydroxypropyl perfluorooctanoate (FGOA) to create fluorinated star-shaped block copolymers PMMA-b-poly(FGOA)s with fluorine content ranging from 0 to 31.7 wt %. The polymerizations are well controlled with the polydispersity indices <1.30. The polymers readily dissolve in common organic solvents and show good film-formation. Compared with the nonfluorinated sample, the fluorinated films exhibit significantly increased water contact angles owing to the enrichment of fluorine on the surface. The enhanced hydrophobicity is advantageous for the optical stability when the devices work under a moist environment. Moreover, the films possess high thermo-optic coefficients, tunable refractive indices, and extremely low birefringence coefficients because of the presence of bulky and rigid tetraphenylsilane core and star-shaped topological structure, showing potential application in optical waveguide devices. (C) 2016 Wiley Periodicals, Inc.