Here, we present a facile and robust method for living cationic polymerization using zinc wire as a catalyst precursor. Well-defined poly(vinyl ether)s with various molecular weights and narrow molecular weight distributions ( Đ < 1.10) can be achieved at room temperature. Excellent living characteristics were observed in kinetic and chain extension experiments. Mechanistic investigations revealed that the polymerization was catalyzed by the in situ generation of trace zinc ions, which is the key to polymerization under mild conditions. The utilization of zinc wire offers several advantages, including reusability, easy separation and low metal residue. Furthermore, we extended the application of this method in continuous flow polymerization, opening up a promising avenue for scalable and efficient industrial production under mild conditions.