The use of Piers-Rubinsztajn conditions was explored for the synthesis of silicone polymers bearing pendant triarylamine functionality. We have found that up to 60% of the hydride groups of a silicone copolymer can be successfully substituted with a triarylamine moiety, without metathesis or redistribution of the silicone. The resulting polymers are hydrolytically stable. The functionalization procedure is straightforward, conducted under ambient conditions with a simple one-step work-up, and avoids the use of a metal-based catalyst. The resulting phenylated triarylamine-silicone hybrid polymer was characterized by optical absorption and fluorescence spectroscopy, CV, and differential scanning calorimetry. The hybrids maintain the physical appearance of a silicone polymer while adopting the photophysical and electrochemical characteristics of the triarylamine.