Radical/Polar Crossover (RPC) chemistry is a rapidly growing subset of photoredox catalysis that is characterized by transformations featuring both radical and ionic modes of reactivity. Net-neutral RPC is particularly interesting in that both the single-electron oxidation and reduction steps occur through interaction with the photocatalyst, thus precluding the need for exogenous oxidants or reductants. As such, these transformations facilitate rapid incorporation of molecular complexity while maintaining mild reaction conditions. This review covers recent advances in photoredox-mediated net-neutral RPC synthetic methods, with a particular emphasis on C-C bond-forming reactions.