AbstractThe simultaneous mitigation of CO2 emissions and direct generation of value‐added chemicals has motivated research in solar‐driven electrochemical CO2 reduction. Here, devices incorporating heterogeneous catalysts that operate under bias‐free aqueous conditions are categorized and compared, encompassing photoelectrochemical (PEC), photovoltaic‐electrochemical (PV‐EC), and combined approaches (PV‐PEC). The best‐performing PEC systems are currently those based on integrated photoelectrodes featuring protective layers. However, the highest overall performances in terms of current density and solar‐to‐carbon efficiency are exhibited by PV‐EC cells that make use of gas‐fed flow cell technology. The advantages of individual components in each device type are assessed to provide future directions for research in solar‐driven CO2 reduction.