<p>Semiconductor biohybrids offer a viable approach to harness solar energy for the biosynthesis of high-value energy-rich long-chain compounds (ERLCCs). However, solar-driven ERLCC biosynthesis routes are often hindered by the inefficient conversion of light energy into cytosolic cofactors. Here we present a design strategy to rewire energy flow in biohybrids, enabling efficient solar-to-ERLCC conversion. Specifically, by tuning the morphology and structure of semiconductors we constructed an intracellular biointerface within engineered heterotrophic <i>Vibrio natriegens</i> chassis. This CdS–<i>V. natriegens</i> biohybrid achieved a solar-to-2,3-butanediol (BDO) conversion efficiency of 2.35%. Multi-omics and biochemical analyses identified an electron mediator, thiamine pyrophosphate, exogenous supplementation of which enhanced cofactor regeneration, further increased the solar-to-BDO efficiency to 2.83% and achieved a carbon yield of 0.497 g g⁻¹. This biohybrid platform was further extended to produce polyhydroxybutyrate and α-farnesene, and upcycle various waste-carbon sources—including mannitol, cellulose, chitosan and industrial wastewater—into BDO. In a 5-l fed-batch bioreactor using wastewater as the sole carbon source, the system achieved a BDO titre of 30.71 g l⁻¹, demonstrating its scalability and robustness. This study establishes a versatile framework for solar-driven microbial biomanufacturing and waste-to-value conversion, paving the way to carbon-efficient chemical production.</p>