The principles and applications of ALE have demonstrated its simplicity and efficacy in tailoring microbial phenotypes for improved industrial performance. Examples of successful ALE applications illustrate the transferability, flexibility and transformative potential of ALE in metabolic engineering and synthetic biology. For example, ALE of Sporomusa ovata integrated with light-harvesting silicon nanowires led to a 2.4-fold increase in CO₂-reducing current density, enhancing bioelectrochemical CO₂ reduction. Similarly, C. autoethanogenum strains developed through ALE showed superior growth and product profiles in continuous bioreactor cultures. ALE using CO₂ and H₂, with other C. autoethanogenum lineages exposed to 2% CO, has also significantly enhanced growth rates and ethanol production, revealing extensive proteome and metabolome changes that highlight new targets for metabolic engineering. Here, we explore for the first time the synergistic potential of ALE-derived gas-fermenting bacteria and photocatalysis for the overall conversion of CO2 to acetate and ethanol (Figure ). A new strain of Clostridium ljungdahlii has been adapted for improved syngas-to-acetate conversion, which is subsequently coupled to a synthetic CO2to-syngas photocatalyst to demonstrate an overall CO2→syngas→acetate domino-reaction. We therefore present a novel and alternative strategy for solar energy conversion to multicarbon chemicals and biomass that harnesses the symbiotic strength of synthetic and biological catalyst.