Site-selective incorporation of fluorocarbon substituents into organic molecules is a field of continuing interest, and a variety of approaches have been reported. The research described within this thesis is concerned with the functionalisation of C-H bonds adjacent to primary or secondary hydroxyl units via free-radical additions to fluoroalkenes. A range of cyclic and acyclic alcohols and diols have been functionalised in this manner, and both substituent and electronic effects on the radical process have been investigated. Further functionalisation of the polyfluoroalkylated products has been performed, giving a range of new fluorinated systems, and an investigation into the chemistry of these systems has begun.