Synthetic photoelectrochemistry (PEC) is receiving increasing attention as a new frontier for the generation and handling of reactive intermediates. PEC permits selective single‐electron transfer (SET) reactions in a much greener way and broadens the redox window of possible transformations. Herein, the most recent contributions are reviewed, demonstrating exciting new opportunities, namely, the combination of PEC with other reactivity paradigms (hydrogen‐atom transfer, radical polar crossover, energy transfer sensitization), scalability up to multigram scale, novel selectivities in SET super‐oxidations/reductions and the importance of precomplexation to temporally enable excited radical ion catalysis. Synthetic photoelectrochemistry (PEC) offers new prospects for the generation and handling of reactive intermediates. PEC permits selective single‐electron transfer (SET) reactions in a much greener way and broadens the redox window of possible transformations. This Review discusses the combination of PEC with other reactivity paradigms, scalability up to multigram scale, novel selectivities in SET super‐oxidations/reductions and the importance of precomplexation.