Newly synthesized fluorinated monomers 4-(N-adamantylamino)-2,3,5,6-tetrafluorostyrene (2) and 2,3,4,5,6-pentafluorostyrene (1) were polymerized in water after complexation with randomly methylated beta-cyclodextrin (RAMEB) without the use of any surfactants or cosolvents. The complex stoichiometries of the RAMEB/monomer complexes were investigated by NMR experiments. Kinetic studies of the homo- and copolymerization with styrene demonstrated a high reactivity of the complexed fluorinated monomers in aqueous solution. Using a semibatch polymerization technique, the use of RAMEB induced formation of stable poly(2,3,4,5,6-pentafluorostyrene) latex particles whereas without RAMEB no spherical particles could be visualized.