Compounds of the group 13 elements boron, aluminium and gallium are routinely employed as Lewis acids in catalysis. The high fluoride-ion affinities of three-coordinate group 13 compounds underpin numerous applications that break and functionalise strong carbon-fluorine bonds. For example, BF3-OEt2 and AlCl3 have been reported as catalysts for the Friedel-Crafts alkylation of arenes with fluoroalkanes. 2 B(C6F5)3 has been shown to catalyse the hydrodefluorination of fluoroalkanes using Et3SiH as a terminal reductant. Similar reactivity has been achieved using aluminium chloride fluoride (ACF), a heterogenous catalyst proposed to contain highly Lewis acid active sites based on aluminium. Aluminium compounds are also competent reagents and catalysts for carbon-heteroatom and carbon-carbon from fluoroalkanes. In the past few years, Frustrated Lewis Pair (FLPs) catalysts based on group 13 compounds have been applied to highly selective catalytic transformations that allow the controlled functionalisation of a single carbonfluorine bond of sp 3 CF3 or sp 2 CF2H groups.