It has been shown that the introduction of fluorine to a bioative molecule causes minimal steric alterations, hence can facilitate interactions of a fluorinated biomolecule with enzyme active sites, receptor recognition sites, transport mechanisms, and other biological systems. At the same time, however, the introduction of fluorine alters significantly the physico-chemical properties of the bioactive molecule because of its large electronegativity.  Thus, this type of modification, in turn, can induce modified biological responses. Rational designs exploiting these special properties of fluorine have been successful in the development of new and effective biochemical tools as well as medicinal and therapeutic agents. Fluorinated congeners can also serve as excellent probes for the investigation of biochemical mechanisms.  ¹⁹F-NMR can provide unique and powerful tools for the mechanistic investigations in biology.  This lecture describes the organofluorine chemistry at the biomedical interface, exploiting the unique nature of this element mentioned above, including taxane anticancer agents as a showcase in this field of research.