Perfluoroalkyl-containing substances (PFAS), have become omnipresent materials in the modern world for both commercial and research applications. Compounds such as perfluoroalkylated arenes and heteroarenes have found uses in surfactants, lubricants, and flame retardants as a result of their astonishing chemical stability. Consequently, the synthesis of such compounds encompasses a large body of scientific articles and patents developed in the previous century. Most recent reviews on this subject have thus focused on summarizing this traditional literature, and have thereby spurred the development of a new wave of reaction manifolds employing modern synthesis principles. This new generation of methodologies focuses on the greener synthesis of perfluoroalkylated aromatic scaffolds, through the use of more efficient organometallic reactions, as well as by photochemical and electrochemical strategies. Herein, we will summarize this cohort of reactions while highlighting current challenges and future desirable outcomes for their environmentally friendly synthesis.