Current CO₂ emission rates are incompatible with the 2 °C target for global warming. Negative emission technologies are therefore an important basis for climate policy scenarios. We show that photoelectrochemical CO₂ reduction might be a viable, high-efficiency alternative to biomass-based approaches, which reduce competition for arable land. To develop them, chemical reactions have to be optimized for CO₂ removal, which deviates from energetic efficiency optimization in solar fuel applications.