A good regioselective, high atom-economical and transition-metal-free method for the synthesis of α-functionalized ether derivatives via the domino radical cyclization of 1,6-enynes is described. A series of α-functionalized ether derivatives could be easily obtained in good yields with wide functional group tolerance by using less toxic and inexpensive Cs2CO3 as the base. The control experiment results show that the reaction involves a radical process. This strategy provides a regioselective way toward the formation of dual C-C bonds in one step.