Integrating light-harvesting materials with microbial biochemistry is a viable approach to produce chemicals with high efficiency from the air, water, and sunlight. Yet it remains unclear whether all absorbed photons in the materials can be transferred through the material-biology interface for solar-to-chemical production and whether the presence of materials beneficially affect the microbial metabolism. Here we report a microbe-semiconductor hybrid by interfacing CO2/N2-fixing bacterium Xanthobacter autotrophicus with CdTe quantum dots for light-driven CO2 and N2 fixation with internal quantum efficiencies of 47.2 ± 7.3% and 7.1 ± 1.1%, respectively, reaching the biochemical limits of 46.1% and 6.9% imposed by the stoichiometry in biochemical pathways. Photophysical studies suggest fast charge-transfer kinetics at the microbe-semiconductor interfaces, while proteomics and metabolomics indicate a material-induced regulation of microbial metabolism favoring higher quantum efficiencies compared to the biological counterparts alone.