In conclusion, our proof-of-concept approach combines for the first time photocatalytic CO2 reduction with biosynthesis with adapted bacteria and thereby provides a blueprint for solar bioproduction of multicarbon products. It highlights the potential of enhancing microorganisms' natural abilities through adaptive evolution and their integration with inorganic catalytic systems. Future efforts will aim to optimize these biological-inorganic hybrid systems by assessing their syngas formation rates, scalability, and advancing genetic and metabolic engineering strategies to fully leverage microbial gas fermentation. This study exemplifies the transformative potential of cross-pollinating biological, materials science and chemistry innovations to tackle pressing global environmental challenges.