This article presents a study on picosecond reactions of excited radical ion super-reductants, focusing on the development of a new excitation strategy inspired by natural photosynthesis to generate highly reducing species. The strategy involves two distinct light absorbers, mimicking photosystems I and II, to produce excited radicals that can activate C(sp²)-Cl and C(sp²)-F bonds. The study provides direct evidence for pre-association between radical ions and substrate molecules, enabling photoinduced electron transfer beyond the diffusion limit. The researchers identified 4,4'-dicyano-p-terphenyl (DCT) and 4,4'-dicyanobiphenyl (DCB) as potentially stronger reductants in their excited radical anionic forms. Using a sensitized ConPET approach, they achieved reduction potentials up to -3.0 V versus SCE, demonstrating the feasibility of extreme reduction potentials in photoredox reactions. The study also highlights the importance of pre-association between radical ions and substrates for efficient photochemical reactions. The findings offer a mechanistic understanding for previous synthetic works and enable more rational future photoredox reaction development. The new excitation strategy pushes the current limits of reactions based on multi-photon excitation and very short-lived but highly redox active species. The study also explores the reactivity of excited organic radicals, showing that the pre-association between radical ions and substrates is crucial for efficient photochemical reactions. The results demonstrate that the newly developed strategy can achieve high yields in photocatalytic reactions, such as the reductive dehalogenation of aryl halides and the intramolecular radical nucleophilic substitution of 2-halide-N-phenylanilines. The study also provides insights into the pre-association between radical ions and substrates, showing that the association constant is significant, indicating a strong interaction between the radical anion and the substrate. The findings suggest that the pre-association is essential for efficient photochemical reactions and could enable new photochemistry beyond the diffusion limit. The study also discusses the implications of the findings for photoredox catalysis, highlighting the potential of the new strategy to complement mainstream approaches aimed at elongating the excited-state lifetimes of photocatalysts. The results demonstrate the effectiveness of the new excitation strategy in achieving high yields in photocatalytic reactions, providing a rational basis for fundamentally new photochemistry beyond current kinetic and thermodynamic limits.This article presents a study on picosecond reactions of excited radical ion super-reductants, focusing on the development of a new excitation strategy inspired by natural photosynthesis to generate highly reducing species. The strategy involves two distinct light absorbers, mimicking photosystems I and II, to produce excited radicals that can activate C(sp²)-Cl and C(sp²)-F bonds. The study provides direct evidence for pre-association between radical ions and substrate molecules, enabling photoinduced electron transfer beyond the diffusion limit. The researchers identified 4,4'-dicyano-p-terphenyl (DCT) and 4,4'-dicyanobiphenyl (DCB) as potentially stronger reductants in their excited radical anionic forms. Using a sensitized ConPET approach, they achieved reduction potentials up to -3.0 V versus SCE, demonstrating the feasibility of extreme reduction potentials in photoredox reactions. The study also highlights the importance of pre-association between radical ions and substrates for efficient photochemical reactions. The findings offer a mechanistic understanding for previous synthetic works and enable more rational future photoredox reaction development. The new excitation strategy pushes the current limits of reactions based on multi-photon excitation and very short-lived but highly redox active species. The study also explores the reactivity of excited organic radicals, showing that the pre-association between radical ions and substrates is crucial for efficient photochemical reactions. The results demonstrate that the newly developed strategy can achieve high yields in photocatalytic reactions, such as the reductive dehalogenation of aryl halides and the intramolecular radical nucleophilic substitution of 2-halide-N-phenylanilines. The study also provides insights into the pre-association between radical ions and substrates, showing that the association constant is significant, indicating a strong interaction between the radical anion and the substrate. The findings suggest that the pre-association is essential for efficient photochemical reactions and could enable new photochemistry beyond the diffusion limit. The study also discusses the implications of the findings for photoredox catalysis, highlighting the potential of the new strategy to complement mainstream approaches aimed at elongating the excited-state lifetimes of photocatalysts. The results demonstrate the effectiveness of the new excitation strategy in achieving high yields in photocatalytic reactions, providing a rational basis for fundamentally new photochemistry beyond current kinetic and thermodynamic limits.