If living poly(vinyl ethers) are terminated with a large excess of methanol, containing aqueous ammonia, well-defined products are obtained. If only a slight excess of methanol is used, aldehydes and coupling products are formed. However, termination with an excess of a hydroxy terminated polymer is cumbersome. According to a given reaction scheme, the termination with methanol in the presence of an anhydrous organic base, should give better results. With two equivalents of triethylamine with respect to the initiator only two equivalents of methanol are needed to give a clean reaction. With this recipe block copolymers of poly(vinyl ether) and poly(ethylene glycol) are prepared.