AbstractPotassium carboxylates and 18‐crown‐6 form initiator systems for the anionic polymerization of oxiranes to afford polyethers with an acyloxy group at one of the chain ends. Because of the slow initiation as compared to the propagation step, the resulting polymers have wide molecular weight distributions (Mw/Mn≈ 4,0). The presence of a small amount of water in the catalysts accelerates the initiation to give polymers with narrow molecular weight distributions (Mw/Mn⩽ 1,2). The polymerization of methyloxirane is accompanied by a significant chain‐transfer reaction to the monomer, especially at high temperatures. Hexamethylcyclotrisiloxane is also polymerized by the same initiators. Furthermore, potassium salts of carboxylic acids initiate the polymerizations in the presence of a cr