A new methodology based on glucose oxidase (GOx) deoxygenation and hydrogen peroxide/vitamin C (H2O2/Vc) redox initiation for conducting RAFT polymerization at low temperature in air is reported. GOx catalyzes reduction of oxygen in the presence of glucose to generate hydrogen peroxide, which is directly used to constitute a redox pair with Vc for the efficient generation of hydroxyl radicals to initiate RAFT polymerization in air. Various experimental parameters including temperature, stirring speed, prepolymerization incubation time, and concentrations of Vc, glucose, and GOx were evaluated with respect to monomer conversion, molecular weight, and dispersity. Efficient removal of oxygen is typically realized within 10 min before polymerization is initiated by addition of Vc, and high conversions are achieved within 5 h. Well-defined homopolymers and block copolymers have been efficiently synthesized with high monomer conversions and low dispersities (< 1.2). Using this new methodology, it is possible to conduct controlled RAFT polymerizations in both open and sealed vessels, though lower conversions but less termination by oxygen are typically observed for the sealed systems. (c) 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 164-174