Electrocatalytic CO₂ reduction coupled with biocatalysis for high-value products

The rising concentration of carbon dioxide (CO₂) has created an urgent need for technologies that can both mitigate emissions and supply sustainable carbon feedstocks. Electrocatalytic carbon dioxide reduction utilizes renewable electricity to convert CO₂ into C₁–C₃ products at high rates under mild conditions, but it remains challenging to produce longer-chain molecules with high selectivity and efficiency. Biocatalytic systems are notable for forging C–C bonds and assembling complex products. However, most organisms fix CO₂ inefficiently and purely biological routes are constrained by thermodynamics and enzyme kinetics. This review examines how integrating electrocatalysis and biocatalysis in cascade systems combines the strengths of both approaches. We discuss the historical development and motivation for these hybrids, summarize recent progress in electrocatalytic CO₂/CO conversion to C₁–C₃ intermediates, and outline biocatalytic strategies that extend short-chain feedstocks to higher-value C_n products. We further examine challenges in catalyst stability, pathway and strain engineering, and process scale-up, and propose directions for advancing electro-biosynthetic manufacturing. Together, these developments point toward a circular carbon economy in which CO₂ becomes a practical starting point for complex carbon-based products.