Rare-earth catalysis has become a hot topic in the field of catalytic organic reaction. Chain ethers mostly have lower reactivity and lower boiling points which limited their reaction scope. Herein, we found a rare-earth Y(OTf)3 can catalyze the coupling reaction of ethers especially chain ethers and thioethers with azaarenes. This protocol features simple operations, a broad substrate scope (31 examples), moderate to good yields (up to 85%), and atom economy.