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Microbial electrosynthesis is potentially a sustainable biotechnology for the conversion of the greenhouse gas CO₂ into carboxylic acids, thus far mostly limited to acetic acid (C2). Despite the environmental benefits of recycling CO₂ emissions to counter global warming, bioelectrochemical production of acetate is not very attractive from an economic point of view. Conversely, carboxylates and corresponding alcohols with longer C content not only have a higher economical value as compared to acetate, but they are also relevant platform chemicals and fuels used on a diverse array of industrial applications. Here, we report on a specific mixed reactor microbiome capable of producing a mixture of C4 and C6 carboxylic acids (isobutyric, n-butyric, and n-caproic acids) and their corresponding alcohols (isobutanol, n-butanol, and n-hexanol) using CO₂ as the sole carbon source and reducing power provided by an …