Fluorinated arylene vinylene ether (FAVE) polymers were prepared from the base-promoted addition of commercial 2,2-bis(4-hydroxyphenyl)hexafluoropropane (6F bisphenol A) to aryl trifluorovinyl ether (TFVE), 2,2'-bis(4-trifluorovinyloxybiphenyl)-1,1,1,3,3,3-hexafluoropropane. The step-growth polymerization kinetics by using stoichiometric NaH and catalytic Cs(2)CO(3) were investigated by monitoring the (19)F NMR signals of the aryl TFVEs. The nth order kinetic model was used to determine rate constants over a series of programmed temperatures. Polymerization using stoichiometric NaH resulted in second-order kinetics with an activation energy of 59 kJ/mol. This model kinetic study provided insight into the mechanistic pathways of the FAVE polymer system that has recently shown a lot of interest in many areas of materials science. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4441-4447, 2011