Summary: In this paper we show how the strong organic Lewis acid catalyst, tris(pentafluorophenyl)borane (B(C6F5) or BCF), can be used to facilitate the functionalization of simple polymeric silicones with a triarylamine yielding a novel class of charge transporting materials. The reaction conditions we refer to as Piers-Rubinsztajn Conditions and we have previously shown such conditions to be suitable when using phenylated silicones as precursors. In this work we found they also work successfully for a silicone oligomer as well as cocopolymers of polymethylhydridosiloxane (PMHS) and polydimethylsiloxane (PDMS) and a PMHS homopolymer, all of which are highly abundent and available in industrial quanitities. The resulting material was either a waxy solid, viscous oil or a glass. An additional “finishing” step with anisole using the same chemistry was found necessary to prevent gelation of the copolymer and homopolymer of PMHS. Even after finishing a small fraction (<5%) of Si-H groups remained in the silicones. This nonetheless provides a rapid and mild method to synthesize functional silicones and tune their physical properties, using commonly available starting materials.