Aqueous Fenton-reversible addition-fragmentation chain transfer (RAFT) polymerization catalyzed by heterogeneous catalysts, that is, Fe(II) metal-organic framework (MOF) particles, coupled with hydrogen peroxide (H2O2) with the reaction mixture exposed to air in open vessels is reported. Reactive hydroxyl radicals are generated via a heterogeneous redox reaction between Fe(II) of the MOF particles and H2O2, which then chemically deoxygenate the reaction mixture in situ, initiating RAFT polymerization. Well-controlled polymers (D < 1.1) with experimental molecular weights close to theoretical values at high monomer conversions (ca. 85%) were achieved within 15 min. High "livingness" of the synthesized polymer chains was demonstrated by chain extension experiments and matrix-assisted laser desorption/ionization time-of-flight analysis. This study contributes to the growing interest in nonenzymatic deoxygenation techniques via heterogeneous catalysis for conducting radical polymerization reactions.