Single electron transfer (SET) processes – frequently utilized by Nature to activate its substrates – significantly enhance the reactivity of organic molecules. These SET reactions provide facile access neutral radicals – reactive intermediates that are particularly attractive for use in complex settings as a consequence of their general lack of reactivity with polar functional groups. The use of redox catalysis (e.g. photocatalysis and electrocatalysis) furthers the benefits of SET processes enabling the reduction of stoichiometric waste byproducts and toxic or hazardous reagents compared with classical approaches. The evolution of our program directed toward a sustainable approach to the upgrading of lignin from its photocatalytic origins to the rationale design of novel HAT electrocatalysts will be described in this talk.