The anionic polymerization of ethylene oxide initiated by alkali metal-based initiators suffers from low polymerization rates even in polar media. We found that the addition of triisobutylaluminum to initiators like alkali metal alkoxides or tetraalkylammonium salts strongly enhances the ethylene oxide polymerization rate, while keeping its living character. At ratio [i-Bu3Al]/[initiator] = 1.5, the controlled synthesis of poly(ethylene oxide) of relatively high molar masses is achieved in short time at room temperature in dichloromethane or toluene. Beside the formation of an aluminate 1:1 complex involving i-Bu3Al and the initiator, a second complex between the trialkylaluminum and the oxirane is formed, which strongly increases the reactivity of the epoxide monomer. Gradient di- and triblock ethylene oxide/propylene oxide copolymers of high molar mass are readily prepared with this system.