Living cell-mediated reversible deactivation radical polymerization is valuable for the construction of engineered living materials, but microorganisms-activated reversible addition-fragmentation chain transfer (RAFT) polymerization without end-group heterogeneity was not yet established. Here, the authors develop an electroactive microorganism-triggered RAFT polymerization system using Shewanella oneidensis-secreted electron shuttle flavins as the electron mediators to directly reduce chain-transfer agents to continuously generate radicals, thus initiating RAFT polymerization.