The article explores the picosecond reactions of excited radical ion super-reductants, addressing the long-standing controversy over their catalytic activity. The authors provide direct evidence for pre-association between radical ions and substrate molecules, enabling photoinduced electron transfer beyond the diffusion limit. They develop a strategy inspired by natural photosynthesis, using two distinct light absorbers to generate excited radicals with extreme reduction power, capable of activating C(sp²)—Cl and C(sp²)—F bonds. This approach overcomes the limitations of classical photochemistry, which relies on nanosecond excited-state lifetimes for diffusion-controlled reactions. The study demonstrates the feasibility of using excited radical ions as catalytically active species, providing a mechanistic understanding that can guide future photoredox reaction development. The findings open new avenues for photochemistry beyond the current kinetic and thermodynamic limits.The article explores the picosecond reactions of excited radical ion super-reductants, addressing the long-standing controversy over their catalytic activity. The authors provide direct evidence for pre-association between radical ions and substrate molecules, enabling photoinduced electron transfer beyond the diffusion limit. They develop a strategy inspired by natural photosynthesis, using two distinct light absorbers to generate excited radicals with extreme reduction power, capable of activating C(sp²)—Cl and C(sp²)—F bonds. This approach overcomes the limitations of classical photochemistry, which relies on nanosecond excited-state lifetimes for diffusion-controlled reactions. The study demonstrates the feasibility of using excited radical ions as catalytically active species, providing a mechanistic understanding that can guide future photoredox reaction development. The findings open new avenues for photochemistry beyond the current kinetic and thermodynamic limits.