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The TiIIICp2Cl‐catalyzed radical ring opening of epoxides produces Ti alkoxides which initiate the ring‐opening polymerization of ε‐caprolactone. A linear dependence of \overlineM_\rmn on conversion, linear kinetics, low \overlineM_\rmw/\overlineM_\rmn values, and the synthesis of block copolymers demonstrate a living process, while NMR spectroscopy confirms the presence of the initiator chain end. Epoxides are thus introduced as a new class of initiators for the Ti‐catalyzed living ring‐opening polymerization of cyclic esters. The TiCp2Cl‐catalyzed radical ring opening of epoxides followed by the initiation of the living ring‐opening polymerization of ε‐caprolactone.