Non-phototrophic microorganism-semiconductor systems have been designed for solar-to-chemical conversion. However, the conversion mechanism remains unclear due to the lack of photosensitive enzymes in non-prototrophic pathways. Herein, the mechanism of non-phototrophic Shewanella woodyi to convert solar energy through CaTiO3 is investigated by untargeted metabolism. By controlling the amount of CaTiO3, the extracellular electron transfer pathway of S. woodyi is upregulated in light. Subsequently, the interfacial electron transfer between CaTiO3 and S. woodyi regulates microbial activity through tryptophan metabolism. Notably, the transformation of riboflavin to lumichrome under light is the key step that mediates upregulation of indole-3-acetic acid in tryptophan metabolism. As a result, the glycolysis and tricarboxylic acid cycle is promoted, leading to an increase in biomass. This study advances the understanding of energy harvesting mechanisms in non-prototrophic organisms and provides reference for designing effective semiconductor-microbe systems.