Electrophilic F/CF3/SCF3 transfer reactions have recently emerged as a promising strategy to introduce fluorine substituents to organic compounds at mild conditions with high reactivity and selectivity. Several safe and stable electrophilic reagents have been introduced and have found interesting applications in synthetic chemistry. To control the reactivity and selectivity of these reactions, metal catalysts are typically used in combination with the reagents. Herein, we describe our recent efforts to elucidate the detailed mechanisms and origins of selectivity for a number of metal-catalyzed electrophilic F/CF3/SCF3 transfer reactions using density functional theory calculations. Focus is on reactions employing hypervalent fluoroiodine and nitrogen-based reagents, with zinc or rhodium as the metal catalysts. The roles of the metal ions are discussed, and some novel mechanistic ideas have emerged from these calculations that can have bearing on other reactions for introducing fluorinecontaining groups.