Electrochemical reduction of the perfluoroalkanes n-C6F14, n-C8F18, the branched perfluoro-2,4-dimethyl-3-ethylpentane (C9F20) and its unsaturated analogues as follows : the stable radical perfluoro-2,4-dimethyl-3-ethylpentyl (C9F19), a mixture of two isomers of hexafluoropropylene trimers (C9F18) was investigated. It is established that this process leads to C-F bond splitting and is facilitated with the increase in length, branching and unsaturation of the perfluorocarbon molecules. The products of n-perfluoroalkane reduction were shown to contain polyconjugated bonds and seem to be of a polymeric nature. Reduction of branched C9F20, C9F19, and the C9F18 isomer mixture leads to polymeric products and relatively stable carbanion particle formation.