A library of fluorinated aryl diazomethanes were polymerized using BF3·OEt2 as a catalyst. The polymerization of 2,3,4,5,6-pentafluorophenyl diazomethane was found to be controlled, permitted chain extensions, and facilitated access to a series of block copolymers. Moreover, the polymer chains grew in one carbon increments (so-called "C1 polymerizations") and, as such, afforded highly substituted polymers that featured aryl units pendant to every carbon atom of the backbone. The polymers were characterized using size exclusion chromatography, various spectroscopic techniques, and a series of static and dynamic contact angle measurements. Compared to less-substituted analogues that were prepared using typical C2 polymerization methodologies, the C1 fluorinated polymers were found to be more hydrophobic while maintaining a sufficient solubility to be processed into robust films.