Recently, the understanding of the importance of fluorination in organic compounds has exploded. It provides a handle for medicinal, agricultural and materials chemists to advantageously affect the properties of a molecule. Despite these enhancements, due to the absence of fluorine containing molecules in the natural world, the pool of molecules such as these from which chemists may draw to build larger and more elaborate molecules is very limited. Single fluorines can be installed into molecules, though this process is arduous, expensive, and inefficient. This problem is compounded when sequential fluorination processes are required. From a fundamentally different approach to fluorination in this way, installing fluorines everywhere, perfluorination, is straightforward and reliable. The fluorines may then be substituted one by one to give the desired molecule. It is toward this goal that the Weaver Lab has labored, developing methodology to perform new and interesting transformations on polyfluorinated molecules to not only reduce the fluorine content, but to do it selectively, and increase the complexity of the molecule as desired. Photocatalysis and SNAr can serve in this capacity. Further, photocatalysis can be used in synthesis that does not involve fluorine, but rather take advantage of some of the other novel reactivities in which the photocatalytic cycle can be engaged. Expeditions into these realms are the subjects explored herein.