"Multi-vicinal fluoroalkanes" are straight-chain alkanes in which each adjacent carbon atom is bonded to one fluorine atom. Such molecules may be regarded as intermediate in structure between alkanes and perfluoroalkanes. The alternate fluoromethylene groups also generate stereogenic centres, which need to be controlled during synthesis. This review will describe our recent progress in the preparation of such single isomer motifs and the study of the conformational behaviour of this new class of organofluorine compounds.