Radical cations are key intermediate in oxidation reactions but their reactivity has not been explored in much detail. Our group has begun exploring these reactive intermediates through cyclizations that involve various radical cation trapping groups. Previously, we only utilized electrochemistry to probe the mechanism of these reactions but, recently, we have started to used photochemical methods to study the generality of the trapping groups. What we have seen is that it is important to include the steps in the cyclization mechanism that involve single electron transfers when considering radical cation cyclizations.