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Significance Metabolic engineering benefits from the tunable and tightly controlled transformations afforded by biological systems. However, these reactions have generally been limited to naturally occurring pathways and products. In this work, we coopt metabolic electron transfer fromShewanella oneidensisto control the activity of an exogenous metal catalyst in an abiotic reaction scheme: atom-transfer radical polymerization. In the presence ofS. oneidensis, polymerizations exhibited well-defined kinetics and yielded polymers with controlled molecular weights and low polydispersities. Additionally, polymerization activity was dependent on electroactive metabolism and specific electron transport proteins, both of which provide handles to control material synthesis. This work serves as a proof-of-principle toward expanding the scope of reactions available to metabolic engineers to include previously discovered transition-metal–catalyzed reactions.