This study investigates the role of cage escape in determining the rates and quantum yields of photoredox reactions. The research shows that the escape of oxidized donor and reduced acceptor species from a solvent cage is critical for the formation of photoredox products. Using ruthenium(II) and chromium(III) photocatalysts, the study finds that the cage escape quantum yields significantly influence the reaction rates and quantum yields in three benchmark photoredox reactions: aerobic hydroxylation, reductive debromination, and aza-Henry reaction. The results indicate that the cage escape quantum yield is governed by the relative rates of cage escape and reverse electron transfer within the solvent cage. The study also demonstrates that the quantum yields of photoredox product formation correlate with the cage escape quantum yields, with the Ru(II) complex showing significantly higher cage escape quantum yields compared to the Cr(III) complex. The findings are explained within the framework of Marcus theory for electron transfer, highlighting the importance of cage escape in photoredox catalysis. The study underscores the need for a deeper understanding of the mechanisms underlying photoredox reactions and the role of cage escape in determining their efficiency.This study investigates the role of cage escape in determining the rates and quantum yields of photoredox reactions. The research shows that the escape of oxidized donor and reduced acceptor species from a solvent cage is critical for the formation of photoredox products. Using ruthenium(II) and chromium(III) photocatalysts, the study finds that the cage escape quantum yields significantly influence the reaction rates and quantum yields in three benchmark photoredox reactions: aerobic hydroxylation, reductive debromination, and aza-Henry reaction. The results indicate that the cage escape quantum yield is governed by the relative rates of cage escape and reverse electron transfer within the solvent cage. The study also demonstrates that the quantum yields of photoredox product formation correlate with the cage escape quantum yields, with the Ru(II) complex showing significantly higher cage escape quantum yields compared to the Cr(III) complex. The findings are explained within the framework of Marcus theory for electron transfer, highlighting the importance of cage escape in photoredox catalysis. The study underscores the need for a deeper understanding of the mechanisms underlying photoredox reactions and the role of cage escape in determining their efficiency.