(19)F NMR has been used as a probe for investigating bioorganic and biological systems for three decades. Recent reviews have touted this nucleus for its unique characteristics that allow probing in vivo biological systems without endogenous signals. (19)F nucleus is exceptionally sensitive to molecular and microenvironmental changes and thus can be exploited to explore structure, dynamics, and changes in a protein or molecule in the cellular environment. We show how mass spectrometry can be used to assess and characterize the incorporation of fluorine into proteins. This methodology can be applied to a number of systems where (19)F NMR is used.