AbstractMiniaturized solid zinc‐ion batteries that are safe, environmentally friendly, and low‐cost are ideal candidates for powering emerging microelectronics. However, sluggish Zn²⁺ mobility in solid phases hampers the viability of solid Zn²⁺ electrolytes and hence their practicability. Here, nanoscale Zn²⁺ channels are successfully engineered in a plastic‐crystal electrolyte, thus activating fast Zn²⁺ solid‐state transport. The ion‐dipole interaction exerted by water molecules orients amphiphilic anions in bilayers, further forming a layered architecture backed by long‐range van der Waals attractive forces. In the interlayer, the heteroleptic coordination contributed by the water molecule and anion frees the Zn²⁺ from anionic traps, leading to a high Zn²⁺ conductivity of 2.2 × 10⁻³ S cm⁻¹. This elaborately tailored texture confers a combination of robust mechanical characteristics and outstanding electrochemical performance upon the resultant electrolyte. The applicability is demonstrated by the high Zn²⁺ platting/stripping efficiency (99.6%), durable longevity of symmetric Zn‐Zn and Zn‐MnO₂ cells, as well as the engineering of versatile micro batteries (MBs). This work provides new perspectives for developing super multivalent ion conductors through the innovative design of ion‐conducting nanochannels.