Direct radical additions of ethers to terminal alkynes were investigated by using Me2Zn/O2 as radical initiator to afford 2‐vinyl ether derivatives with high E‐selectivity, while reversed E/Z selectivity is obtained with Et3B/O2. Two competitive pathways are suggested for the formation of vinyl radical B: zinc‐radical exchange (route a) followed by protonation provides E‐configuration products exclusively through Zn(II) complexation. Hydrogen abstraction by vinyl radicals (route b) yields mainly Z isomers.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)