The anionic ring-opening polymerization of cyclosiloxanes is one important route for synthesizing polyorganosiloxanes and several different initiators are well known. In the scope of this work especially N-Heterocyclic carbenes as well as amines, amidines and guanidines were investigated as suitable initiators and coinitiators respectively. The proposed mechanism which includes the activation of an alcohol, was extended leading to a α-, ω-di(alkoxydimethylsilyl) endcapped silicone. Influencing parameters such as reaction parameters, the nature of the solvent and the alcohol were investigated.