The unique properties imparted by planar, rigid aromatic rings in synthetic polymers make these macromolecules useful in a range of applications, including disposable packaging, aerospace materials, flexible electronics, separation membranes, and engineering thermoplastics. The thermal and chemical stability of aromatic polymers, however, makes it difficult to alter their bulk and/or surface properties and results in challenges during recycling. In response, we report a platform approach for the C-H functionalization of aromatic polymers by taking advantage of their innate reactivity with electrophilic radical intermediates. The method uses mild reaction conditions to photocatalytically generate electrophilic fluoroalkyl radicals for the functionalization of an array of commercially relevant polyaromatic substrates, including post-industrial and post-consumer plastic waste, without altering their otherwise attractive thermomechanical properties. The density of fluorination, and thus the material properties, is tuned by either increasing the reagent concentration or incorporating longer perfluoroalkyl species. Additionally, the installation of versatile chemical functionality to aromatic polymers is demonstrated through the addition of a bromodifluoromethyl group, which acts as an initiator for atom transfer radical polymerization (ATRP) grafting of vinyl polymers. The method described herein imparts new and versatile chemical functionality to aromatic polymers, enabling an efficient approach to diversify the properties of these otherwise recalcitrant commodity plastics and demonstrating a viable pathway to upcycle post-consumer plastic waste.