The salt Fe(OTf)3 has been shown to function as an effective catalyst in three different reactions, epoxide oxidative ring-opening to an α-hydroxy ketone, urea α-diketone condensation to form glycolurils, and glycoluril diether synthesis by formaldehyde condensation. In each of these reactions, Fe(OTf)3 was compared to Bi(OTf)3, a viable alternative catalyst with few or no prior examples of this type. Differences and advantages are highlighted but in most cases yields were generally high, and both catalysts outperformed conventional acid catalyzed methods.