Highly branched perfluorinated aromatic polyether copolymers were prepared from the polycondensation of the AB(2) monomer, 3,5-bis[(pentafluorobenzyl)oxy]benzyl alcohol with a variety of fluoroaryl and alkyl bromide AB comonomers. The structures and comonomer distribution of the resulting polymers were characterized in detail. H-1 NMR data from kinetic trials illustrated that perfluoroaryl AB comonomer distribution correlated to AB comonomer sterics. F-19 NMR data revealed that fluorinated AB monomers and 3-bromo-1-propanol AB monomers were distributed within the AB(2) polymer backbone, while longer alkyl bromide AB monomers, 6-bromo-1-hexanol, were mostly distributed along hyperbranched polymer chain ends. In general, as AB comonomer incorporation increased for nonsterically hindered copolymers, thermal decomposition onset increased and glass transition temperatures decreased. The combined data demonstrated the effect of comonomer distribution and sterics on physical properties of AB(2)-based polymer systems. The resulting materials were used to cast thin polymer films for measurement of contact angle, which were shown to be directly related to comonomer content. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1880-1894