Recent protocols and reactions for catalytic radical perfluoroalkylations will be described. The production of perfluoroalkyl radicals (RF = C n F2n+1, n ≥ 2), which effect both addition and substitution reactions on organic substrates, can be realized through a range of diverse methods such as the well-established visible-light transition-metal-mediated photocatalysis, organic-dye-photocatalyzed reactions, electron donor–acceptor complexes, and more recently frustrated Lewis pairs. Thus, perfluoroalkylation reactions of carbon–carbon multiple bonds, isocyanides, nitrones, hydrazones, β-keto esters, α-cyano arylacetates, sulfides, and (hetero)­arenes will be described. Special emphasis will be placed on examples published after 2015, where higher fluorinated series of fluoroalkylating reagents are studied.