| Summary: | Abstract Metal‐Organic Frameworks (MOFs) hold great potential to be used as porous (photo)‐electrocatalytic platforms containing large concentration of immobilized molecular catalysts. Indeed, the use of MOFs in a photo‐electrochemical devices was recently demonstrated. However, so far there are no reports of MOFs used for photo‐electrochemical O2 reduction to H2O2. Herein, we utilize a Co‐porphyrin based MOF (Co‐MOF‐525), that produces H2O2 at high faradaic efficiency (95 %), both electrochemically and photo‐electrochemically. Electrochemical characterization show that the active catalytic site is a MOF‐tethered Co(I)‐porphyrin. Additionally, under light illumination, the MOF's intrinsic catalytic rate is significantly accelerated compared to dark electrolysis conditions. Thus, this work could open a path for future implementation of photoactive MOFs in solar fuel schemes.
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