C-F bond activation of aliphatic fluorides provides new methodologies for synthesis of new fluorinated building blocks as well as versatile non-fluorinated products. This review covers the recent C-F bond cleavage examples and further transformation of compounds bearing with an aliphatic fluoride, difluoromethylene group or trifluoromethyl groups. The methods to activate a C-F bond include activation by Lewis acid, Bronsted superacids and hydrogen bonding, and mediation by transition-metals and rare earth metals. Partial reduction of trifluoromethyl group through a single electron transfer (SET) process can provide the compounds with less fluorine. Bases are often used for the elimination of hydrofluoride. S(N)2' displacement is also an important method for transformation of monofluorinated, difluorinated and trifluorinated olefins to various synthetically interesting molecules. (C) 2015 Elsevier B.V. All rights reserved.