Metallic zinc anodes in zinc‐ion batteries suffer from problematic Zn dendrite chemistry. Previous works have shown that preferred‐orientation crystal planes can help dendrite‐free metal anodes. This work reports a nanothickness (≈570 nm) AgZn3 coating to regulate the Zn growth. First, AgZn3@Zn anode avoids the problem, in Ag@Zn anode, that the rate of electrochemical Ag‐Zn alloying is slower than that of Zn dendrites growth. Batteries life increased from 112 h (pure Zn) and 932 h (Ag@Zn) to 1360 h (AgZn3@Zn) at 2 mA cm−2 and 1 mAh cm−2. Then, plasma sputtering can remove nonconductive ZnO and improve Zn‐ion affinity, which brings a longer life for AuZn3@Zn (423 h), CuZn3@Zn (385 h), and AgZn3@Zn (1150 h) than pure Zn (93 h) at 1 mAh cm−2. More importantly, AgZn3 (002) has a high matching with the Zn (002), which can guide ordered Zn epitaxial deposition, thereby achieving dense and dendrite‐free Zn growth. This work clearly captures the fascinating structure of the densely stacked Zn layers on the AgZn3 layer. This strategy not only improves the performance of zinc‐ion batteries greatly but will also help one understand the matching mechanism of the (002) vertical crystal plane. A thin and uniform AgZn3 coating is obtained on Zn foils by Ar plasma sputtering, and is used as the metal anode of aqueous zinc‐ion batteries. Due to its unique vertical crystal plane matching mechanism between AgZn3 (002) and Zn (002), dense and plate Zn deposition and long battery cycle life are achieved.