The growing demand for energy and the excessive use of fossil fuels represents one of the main challenges for humanity. Storing solar energy in the form of chemical bonds to generate solar fuels or value-added chemicals without creating additional environmental burdens is a key requirement for a sustainable future. Here we use biomimetic artificial photosynthesis and present a dPCN-224(H) MOF-based photocatalytic system, which uses reactive oxygen species (ROS) to activate and convert CO2 to ethanol under atmospheric conditions, at room temperature and in 2-5 h reaction time. The system provides a CO2-to-ethanol conversion efficiency (CTE) of 92%. Furthermore, this method also allows the conversion of CO2 through direct air capture (DAC), making it a rapid and versatile method for both dissolved and gaseous CO2.