This work demonstrates the potential of organic-based PEC devices towards long-term water splitting and CO2 reduction. Accordingly, OPV|GE|Pt photocathodes can operate for over 12 days in a neutral buffer solution, attaining a benchmark photocurrent of -17 mA cm -2 at 0 V vs. RHE and onset potential of 1 V vs. RHE. This high photovoltage enables PCE10:EH-IDTBR photocathodes to expand the reaction scope beyond water splitting, attaining unassisted CO2 reduction over 96 h when combined with BiVO4 photoanodes. These standalone PEC devices based on organic semiconductors, carbonaceous encapsulants and molecular CO2 reduction catalysts approach the efficiency and composition of natural leaves, establishing earth abundant artificial leaves as a path towards a nature inspired, circular fuel economy.